61
Fig.3, L=PtBu3, Step 1a(Thermolysis), C21H36ClOPPd, Electronic Energy:-1825.684087 a.u., Gibbs Free Energy: -1825.222384 a.u., Corrected Gibbs Free Energy: -1825.218630 a.u.
P         -2.19956       -0.04159        0.06609
Pd         0.17712        0.06239       -0.30196
C          3.12696        0.56531        0.66619
C          2.35135        0.57130       -0.63771
H          3.04623        1.55005        1.16271
H          2.68621       -0.17850        1.35549
H          2.71796        1.32919       -1.34989
H          2.38604       -0.40176       -1.15908
C          5.53628        1.24365        0.27181
C          4.57599        0.23367        0.42106
C          4.98466       -1.10139        0.28334
C          6.31553       -1.41883        0.01343
C          7.26391       -0.40282       -0.12875
C          6.86944        0.92999        0.00117
H          5.23193        2.29349        0.37542
H          4.24127       -1.90251        0.39332
H          6.61669       -2.46885       -0.08436
H          8.31103       -0.65066       -0.33920
H          7.60736        1.73425       -0.10629
Cl         0.62360       -2.36265       -0.24701
C          0.73566        1.80876       -0.38386
O          0.93231        2.95488       -0.35405
C         -2.50924       -0.95928        1.73232
C         -2.50490       -2.48015        1.57547
C         -1.31425       -0.60734        2.62974
C         -3.81081       -0.57876        2.43442
H         -3.44433       -2.86181        1.14592
H         -1.65161       -2.84802        0.98330
H         -2.41802       -2.91964        2.58795
H         -1.15328        0.47520        2.75838
H         -1.48428       -1.03625        3.63649
H         -0.37943       -1.04485        2.23289
H         -3.94681       -1.25126        3.30328
H         -3.80403        0.44841        2.83250
H         -4.69647       -0.70305        1.78644
C         -2.96512       -0.87516       -1.49414
C         -2.12095       -0.40138       -2.68639
C         -2.83356       -2.39911       -1.46455
C         -4.43456       -0.53720       -1.73099
H         -2.05661        0.69229       -2.79173
H         -1.08918       -0.79576       -2.62594
H         -2.57165       -0.79416       -3.61843
H         -3.58402       -2.88002       -0.81963
H         -3.01586       -2.76946       -2.49171
H         -1.82642       -2.73601       -1.16698
H         -4.80662       -1.15445       -2.57156
H         -5.06818       -0.76566       -0.85527
H         -4.59416        0.51468       -2.01851
C         -2.89452        1.75288        0.21987
C         -2.16819        2.44438        1.37879
C         -2.57218        2.50557       -1.07565
C         -4.39974        1.91815        0.46769
H         -2.50609        2.08098        2.36373
H         -1.07096        2.33673        1.33481
H         -2.39477        3.52704        1.34505
H         -3.23159        2.20456       -1.90723
H         -2.74255        3.58613       -0.90950
H         -1.52684        2.38583       -1.40758
H         -4.62139        3.00260        0.44937
H         -5.03361        1.45652       -0.30165
H         -4.73014        1.55144        1.44862
61
Fig.3, L=PtBu3, Step 1, C21H36ClOPPd, Electronic Energy:-1825.7278568 a.u., Gibbs Free Energy: -1825.263917 a.u., Corrected Gibbs Free Energy: -1825.260223 a.u.
P          2.08392        0.36813        0.12061
Pd         0.33849       -1.16305       -0.04120
C         -3.39982       -0.21271       -1.18317
C         -2.11470        0.29261       -0.51935
H         -3.44084        0.16741       -2.21864
H         -3.35009       -1.31543       -1.24126
H         -2.06215        1.39871       -0.56897
H         -2.08720        0.01717        0.54842
C         -5.35257        1.34370       -0.78273
C         -4.62015        0.20659       -0.41611
C         -5.02880       -0.51431        0.71608
C         -6.14140       -0.11483        1.45619
C         -6.86524        1.01845        1.07739
C         -6.46700        1.74664       -0.04495
H         -5.04490        1.91869       -1.66593
H         -4.46137       -1.40661        1.01443
H         -6.44864       -0.69476        2.33486
H         -7.74169        1.33207        1.65679
H         -7.03075        2.63622       -0.35088
Cl        -1.19115       -3.04694        0.04013
C         -0.89276       -0.23370       -1.24259
O         -0.76415       -0.23445       -2.43407
C          3.25252        0.22979       -1.38888
C          3.91513       -1.15052       -1.38479
C          2.40355        0.26833       -2.66444
C          4.33294        1.30749       -1.45416
H          4.66297       -1.28453       -0.58728
H          3.16966       -1.96462       -1.31527
H          4.44773       -1.28132       -2.34586
H          1.83973        1.20145       -2.80880
H          3.07741        0.15745       -3.53588
H          1.67942       -0.56369       -2.69048
H          5.01368        1.07914       -2.29710
H          3.91996        2.31206       -1.64536
H          4.95106        1.35896       -0.54242
C          2.97799       -0.28361        1.68677
C          2.19414        0.14965        2.92783
C          2.90530       -1.81726        1.66568
C          4.42933        0.16769        1.83497
H          2.30917        1.21916        3.16419
H          1.11626       -0.08407        2.84265
H          2.58223       -0.41208        3.79869
H          3.40333       -2.28877        0.80680
H          3.39002       -2.21072        2.58001
H          1.85605       -2.17897        1.69476
H          4.81610       -0.18911        2.80944
H          5.09347       -0.24710        1.05934
H          4.53901        1.26502        1.82553
C          1.56974        2.19070        0.39541
C          1.10946        2.77612       -0.94240
C          0.36011        2.22827        1.34035
C          2.67389        3.07858        0.96973
H          1.93407        2.92046       -1.65871
H          0.32737        2.16500       -1.42873
H          0.67132        3.77468       -0.75631
H          0.63239        2.12142        2.40030
H         -0.14175        3.20929        1.23982
H         -0.38367        1.44743        1.10394
H          2.29162        4.11528        1.04315
H          2.97333        2.77958        1.98780
H          3.57919        3.11122        0.34236
60
Fig.3, L=PtBu3, Step 2,C21H36OPPd, Electronic Energy:  -1365.459201 a.u., Gibbs Free Energy: -1364.994147 a.u., Corrected Gibbs Free Energy: -1364.990203 a.u.
P          2.11544        0.06553        0.02553
Pd        -0.11873        0.38992       -0.46869
C         -3.35821       -0.84247        0.70247
C         -2.38912       -0.68148       -0.47480
H         -3.43695       -1.91991        0.93201
H         -2.92333       -0.34971        1.59048
H         -2.74367       -1.21515       -1.37754
H         -2.33586        0.39369       -0.77233
C         -5.70147       -1.05156       -0.21288
C         -4.71079       -0.26723        0.39401
C         -4.99628        1.07758        0.66893
C         -6.24041        1.62353        0.35189
C         -7.22032        0.83111       -0.24951
C         -6.94700       -0.50890       -0.53083
H         -5.49145       -2.10623       -0.43358
H         -4.22953        1.70327        1.14474
H         -6.44803        2.67582        0.57985
H         -8.19951        1.25785       -0.49663
H         -7.71221       -1.13904       -0.99964
C         -1.02825       -1.25872       -0.13640
O         -0.75147       -2.35568        0.23075
C          2.74909        1.87450       -0.03688
C          2.10828        2.57744       -1.24227
C          2.22895        2.61240        1.19940
C          4.26698        2.01622       -0.12571
H          2.43732        2.19676       -2.21863
H          0.99937        2.53874       -1.21624
H          2.37923        3.64948       -1.20585
H          2.70946        2.29695        2.13839
H          2.44455        3.69062        1.07804
H          1.13243        2.50945        1.30939
H          4.52524        3.09133       -0.06940
H          4.80135        1.51019        0.69434
H          4.67058        1.64177       -1.08102
C          2.97365       -0.99548       -1.30604
C          2.13233       -2.25227       -1.55398
C          2.98787       -0.22830       -2.62997
C          4.40743       -1.38347       -0.94305
H          2.02313       -2.90728       -0.67794
H          1.12002       -1.99291       -1.91318
H          2.62362       -2.84799       -2.34650
H          3.69555        0.61606       -2.63660
H          3.31350       -0.92239       -3.42734
H          1.98381        0.14118       -2.91030
H          4.85893       -1.91038       -1.80538
H          5.04643       -0.51184       -0.72488
H          4.46473       -2.07196       -0.08465
C          2.39861       -0.67506        1.76822
C          1.28891       -0.17428        2.70030
C          2.27058       -2.20057        1.73144
C          3.76868       -0.32052        2.34779
H          1.28270        0.91548        2.84834
H          0.28802       -0.47513        2.33926
H          1.43343       -0.63457        3.69625
H          3.08934       -2.69660        1.18722
H          2.31692       -2.56715        2.77416
H          1.30818       -2.53473        1.31194
H          3.88921       -0.85305        3.31053
H          4.60237       -0.63487        1.69760
H          3.88545        0.75353        2.56324
66
Fig.3, L=PtBu3, Step 3,C23H42NOPPd, Energy: -1498.110118 a.u. Gibbs Free Energy: -1497.604897 a.u., Corrected Gibbs Free Energy: -1497.600731 a.u.
P         -1.50054       -0.99326        0.03460
C         -0.87746       -1.74755       -1.61242
C         -0.92569       -2.05734        1.51609
C         -3.42720       -0.94710        0.04446
C          0.57512       -2.20292       -1.46570
H          0.95696       -2.46530       -2.47024
H          0.69357       -3.09934       -0.83684
H          1.22769       -1.40934       -1.07176
C         -0.88013       -0.63543       -2.66757
H         -0.50150       -1.04900       -3.62188
H         -0.21335        0.19790       -2.37555
H         -1.87627       -0.21298       -2.86969
C         -1.69724       -2.93902       -2.10870
H         -1.19951       -3.35364       -3.00615
H         -2.72075       -2.66873       -2.41324
H         -1.75976       -3.75447       -1.36877
C         -3.89371       -0.32292       -1.27557
H         -4.98188       -0.13571       -1.20961
H         -3.74098       -0.98711       -2.14108
H         -3.40943        0.64475       -1.49022
C         -4.10528       -2.31113        0.19281
H         -5.19930       -2.15748        0.11582
H         -2.13671       -3.84191        1.02233
H         -3.82552       -3.03464       -0.58876
C         -3.91649       -0.05205        1.20235
H         -4.87835        0.41363        0.91733
H         -3.22956        0.77030        1.46401
H         -4.10535       -0.62640        2.12168
C         -1.10705       -3.56027        1.29267
H         -3.92430       -2.77430        1.17616
H         -0.86444       -4.08537        2.23647
H         -0.43125       -3.96528        0.52237
C         -1.71620       -1.63799        2.75789
H         -2.75550       -2.00011        2.74886
H         -1.72232       -0.54239        2.90569
H         -1.23215       -2.08480        3.64648
C          0.54424       -1.77070        1.82586
H          0.83838       -2.36961        2.70838
H          0.70480       -0.70803        2.08281
H          1.23091       -2.04657        1.01142
Pd        -0.83664        1.24754        0.17086
C          3.60781        1.40641        0.37954
C          2.35388        0.64272       -0.01159
H          3.61763        2.38051       -0.14486
H          3.55606        1.66273        1.45478
C          1.09722        1.38935        0.24855
H          2.33323        0.43570       -1.10055
H          2.29558       -0.34321        0.47391
C          6.10801        1.28782        0.48970
C          4.89999        0.68232        0.10520
C          4.96124       -0.56865       -0.52314
C          6.18942       -1.19309       -0.76059
C          7.37931       -0.57891       -0.37480
C          7.33293        0.66876        0.25365
H          6.07890        2.26736        0.98431
H          4.04299       -1.07802       -0.83874
H          6.21079       -2.17221       -1.25388
H          8.34186       -1.06947       -0.56129
H          8.26131        1.16356        0.56336
O          1.00683        2.58274        0.46190
C         -3.35911        3.41996       -0.31457
C         -4.28143        4.49548       -0.54963
H         -5.13721        4.41848        0.14110
H         -3.78192        5.46522       -0.39020
H         -4.65499        4.45338       -1.58595
N         -2.62039        2.54361       -0.12839
66
Fig.3, L=PtBu3, Step 4,C23H45NOPPd, Electronic Energy: -1498.085827 a.u.Gibbs Free Energy: -1497.582658 a.u., Corrected Gibbs Free Energy: -1497.578235 a.u.
P          2.25621       -0.03353        0.07255
Pd        -0.12425       -0.20974       -0.31471
C         -3.02623       -0.73828        0.67346
C         -2.27222       -0.78910       -0.64224
H         -2.89326       -1.68983        1.22082
H         -2.61111        0.06051        1.31506
H         -2.62609       -1.59436       -1.30662
H         -2.35027        0.14550       -1.22723
C         -5.37366       -1.55110        0.19662
C         -4.49169       -0.48647        0.43002
C         -4.99473        0.82144        0.37887
C         -6.34333        1.05963        0.11190
C         -7.21256       -0.00983       -0.11353
C         -6.72285       -1.31689       -0.07065
H         -4.99352       -2.58056        0.23199
H         -4.31505        1.66554        0.55869
H         -6.72004        2.08912        0.08322
H         -8.27318        0.17544       -0.32041
H         -7.39922       -2.16269       -0.24319
C         -0.61844       -1.97565       -0.40622
O         -0.75121       -3.12794       -0.38850
C          2.48428        0.87375        1.75535
C          2.38287        2.39349        1.62535
C          1.30783        0.42885        2.63599
C          3.80411        0.56535        2.45878
H          3.29695        2.84392        1.20948
H          1.51702        2.72834        1.03286
H          2.25830        2.80868        2.64344
H          1.22256       -0.66285        2.75355
H          1.43780        0.85865        3.64794
H          0.34375        0.80058        2.24026
H          3.89088        1.22403        3.34407
H          3.86293       -0.46986        2.83038
H          4.68166        0.76357        1.81826
C          2.97059        0.86810       -1.47117
C          2.14831        0.37393       -2.67028
C          2.76423        2.38246       -1.41127
C          4.45524        0.61089       -1.71510
H          2.15288       -0.71834       -2.80374
H          1.09350        0.70131       -2.59610
H          2.56752        0.81790       -3.59373
H          3.47917        2.88664       -0.74476
H          2.93971        2.78368       -2.42734
H          1.74060        2.67249       -1.12418
H          4.79398        1.26285       -2.54312
H          5.07667        0.85317       -0.83457
H          4.66644       -0.42553       -2.02404
C          3.02583       -1.79267        0.19798
C          2.33279       -2.53444        1.34592
C          2.73547       -2.53521       -1.11067
C          4.53701       -1.88543        0.44303
H          2.65866       -2.17433        2.33606
H          1.23170       -2.47411        1.30574
H          2.60618       -3.60506        1.29119
H          3.37837       -2.18984       -1.93768
H          2.95482       -3.60943       -0.96353
H          1.68479       -2.45673       -1.43871
H          4.80929       -2.95807        0.42499
H          5.14515       -1.39468       -0.32899
H          4.85090       -1.50160        1.42303
C         -0.98359        2.97936       -0.22120
C         -1.50143        4.31655       -0.16748
H         -1.29163        4.76129        0.81939
H         -1.02496        4.93551       -0.94567
H         -2.59122        4.31050       -0.33359
N         -0.54539        1.90586       -0.25969
66
Fig.3, L=PtBu3, Step 5,C23H45NOPPd, Electronic Energy:  -1498.106229 a.u.,Gibbs Free Energy: -1497.600252 a.u., Corrected Gibbs Free Energy: -1497.596830 a.u.
P         -1.58885        0.54734        0.06301
C         -1.88050        0.44469        1.94853
C         -1.41326        2.40009       -0.41759
C         -3.06603       -0.23324       -0.87950
C         -0.90567        1.38769        2.65857
H         -0.92723        1.15894        3.74093
H         -1.17994        2.44900        2.55482
H          0.13744        1.25619        2.31873
C         -1.53365       -0.96736        2.42990
H         -1.71382       -1.02088        3.52063
H         -0.46582       -1.19793        2.26159
H         -2.13423       -1.76289        1.96243
C         -3.30515        0.80093        2.37655
H         -3.34723        0.81270        3.48296
H         -4.05577        0.06897        2.03836
H         -3.62489        1.79712        2.03059
C         -3.50541       -1.53753       -0.20807
H         -4.26128       -2.01639       -0.85890
H         -3.98123       -1.39225        0.77416
H         -2.68000       -2.25812       -0.09643
C         -4.29072        0.67233       -1.00336
H         -5.10336        0.10097       -1.49198
H         -3.52642        3.03196       -0.19528
H         -4.67450        1.00977       -0.02564
C         -2.56310       -0.62144       -2.27611
H         -3.39223       -1.09609       -2.83527
H         -1.73926       -1.35839       -2.21960
H         -2.21230        0.22964       -2.87966
C         -2.51220        3.32009        0.12161
H         -4.11008        1.56058       -1.62987
H         -2.32825        4.34115       -0.26514
H         -2.50181        3.39569        1.22101
C         -1.41997        2.49850       -1.94732
H         -2.41105        2.29567       -2.38405
H         -0.69292        1.82544       -2.43596
H         -1.15019        3.53109       -2.23690
C         -0.05957        2.93565        0.09773
H          0.34367        3.67672       -0.61696
H          0.71462        2.16229        0.23556
H         -0.15903        3.45222        1.06485
Pd         0.47343       -0.72548       -0.69147
C          3.13712       -1.90040       -0.03530
C          2.23103       -1.82115       -1.24716
H          2.61334       -2.40085        0.80114
H          4.00093       -2.54993       -0.29225
H          2.74659       -1.37218       -2.11443
H          1.83073       -2.80382       -1.54992
C          2.94389        0.18305        1.38095
C          3.63707       -0.55080        0.40628
C          4.74462        0.04434       -0.21095
C          5.14445        1.33863        0.12758
C          4.43927        2.06155        1.09200
C          3.33835        1.47740        1.72252
H          2.07254       -0.27367        1.87276
H          5.29838       -0.51590       -0.97612
H          6.01411        1.78754       -0.36727
H          4.75158        3.07855        1.35706
H          2.78166        2.03540        2.48567
C          1.38837        0.65829       -1.52914
O          2.01064        1.44965       -2.07842
C         -0.47206       -3.62933        0.42529
C         -0.86006       -4.91234        0.93415
H         -1.27225       -4.79941        1.95116
H         -1.63104       -5.35642        0.28274
H          0.00886       -5.58950        0.97174
N         -0.19562       -2.57517        0.03281
60
Fig.3, L=PtBu3, Step 6, C21H39OPPd, Electronic Energy:  -1365.440609 a.u.,Gibbs Free Energy: -1364.976983 a.u., Corrected Gibbs Free Energy: -1364.973921 a.u.
P          1.51076       -0.44853       -0.00058
C          0.78975       -2.15522       -0.47219
C          2.88868        0.02762       -1.24263
C          2.21588       -0.50239        1.77900
C          0.55019       -2.20317       -1.98392
H         -0.05534       -3.10112       -2.21005
H          1.47781       -2.29201       -2.57079
H         -0.01965       -1.32864       -2.34906
C         -0.59540       -2.29186        0.16805
H         -1.01804       -3.27684       -0.10840
H         -1.28523       -1.52229       -0.22204
H         -0.60208       -2.23377        1.26645
C          1.66795       -3.33933       -0.06905
H          1.21495       -4.26795       -0.46675
H          1.74368       -3.46566        1.02336
H          2.69021       -3.27726       -0.47691
C          1.20359       -1.19485        2.69482
H          1.53926       -1.06912        3.74143
H          1.11492       -2.27824        2.51716
H          0.19741       -0.74102        2.62177
C          3.56753       -1.20212        1.90991
H          3.83517       -1.26200        2.98252
H          4.37817       -1.48364       -0.62679
H          3.56032       -2.23304        1.51900
C          2.33112        0.93726        2.29964
H          2.68681        0.90392        3.34722
H          1.35118        1.45242        2.30425
H          3.03938        1.56621        1.74117
C          3.88239       -1.09839       -1.53263
H          4.38187       -0.65161        1.41075
H          4.67661       -0.70545       -2.19627
H          3.42140       -1.94920       -2.06034
C          3.66021        1.23023       -0.69313
H          4.28907        0.98082        0.17627
H          3.00246        2.07416       -0.41684
H          4.34171        1.59811       -1.48271
C          2.25126        0.47568       -2.56444
H          3.02979        0.95827       -3.18459
H          1.44400        1.21581       -2.42190
H          1.84152       -0.35228       -3.15981
Pd        -0.30327        1.22453        0.15372
C         -2.44492        0.86697        1.24456
C         -2.04509        2.19764        0.72961
H         -1.50589        0.16556        1.29128
H         -2.66075        0.88652        2.32829
H         -2.61179        2.60243       -0.12204
H         -1.78548        2.95983        1.47982
C         -4.56614       -0.48858        1.11398
C         -3.48415        0.11287        0.46291
C         -3.37466       -0.01372       -0.92874
C         -4.33068       -0.71921       -1.65663
C         -5.41216       -1.31129       -0.99892
C         -5.52716       -1.19404        0.38638
H         -4.65890       -0.39956        2.20347
H         -2.51573        0.44420       -1.44412
H         -4.22956       -0.81204       -2.74420
H         -6.16482       -1.86804       -1.56916
H         -6.37226       -1.65703        0.90915
C          0.36854        2.73638       -0.71354
O          0.74202        3.69956       -1.21138
60
Fig.3, L=PtBu3, Step 7, C21H40OPPd, Electronic Energy:  -1365.426428  a.u.,Gibbs Free Energy: -1364.966446 a.u., Corrected Gibbs Free Energy: -1364.963440 a.u.
P          1.36482        0.48810        0.00864
C          0.54970        2.14891        0.51031
C          2.70372        0.02643        1.30927
C          2.15491        0.64046       -1.73003
C          0.23143        2.12434        2.00809
H         -0.43004        2.98183        2.23429
H          1.12214        2.23678        2.64595
H         -0.31089        1.20870        2.30856
C         -0.80038        2.31276       -0.19527
H         -1.19413        3.32049        0.03840
H         -1.53738        1.58366        0.18281
H         -0.76243        2.22681       -1.29193
C          1.43063        3.36258        0.20517
H          0.95307        4.26030        0.64180
H          1.53632        3.55329       -0.87526
H          2.44060        3.29069        0.63889
C          1.18736        1.35361       -2.67752
H          1.60222        1.29105       -3.70102
H          1.05669        2.42384       -2.45236
H          0.19255        0.87288       -2.70476
C          3.49207        1.38157       -1.74875
H          3.81790        1.49251       -2.80047
H          4.15445        1.62311        0.81493
H          3.43025        2.39524       -1.32013
C          2.34180       -0.77253       -2.29806
H          2.76901       -0.68854       -3.31554
H          1.37624       -1.30612       -2.39063
H          3.02373       -1.40779       -1.71402
C          3.63472        1.18265        1.68076
H          4.29330        0.83425       -1.22646
H          4.41367        0.79409        2.36438
H          3.11601        1.99109        2.22083
C          3.55256       -1.12290        0.75986
H          4.21213       -0.81815       -0.06797
H          2.94876       -1.98349        0.42102
H          4.20891       -1.48964        1.57063
C          2.03033       -0.48109        2.59144
H          2.80073       -0.96136        3.22313
H          1.24788       -1.23727        2.40310
H          1.57918        0.31776        3.19632
Pd        -0.25151       -1.27828       -0.23823
C         -2.38043       -1.11145       -1.24259
C         -2.00384       -2.41188       -0.85850
H         -0.97383       -0.10049       -1.10403
H         -2.32023       -0.87050       -2.31370
H         -2.43967       -2.86990        0.03911
H         -1.63937       -3.10667       -1.62614
C         -4.07176        0.70384       -1.12078
C         -3.30105       -0.26100       -0.45797
C         -3.40030       -0.36913        0.93862
C         -4.25906        0.46303        1.65096
C         -5.03045        1.41695        0.97999
C         -4.93643        1.53347       -0.40710
H         -3.98747        0.80475       -2.20981
H         -2.77400       -1.09489        1.47463
H         -4.32204        0.37445        2.74158
H         -5.70198        2.07511        1.54331
H         -5.53540        2.28179       -0.93866
C          0.50141       -2.83523        0.65277
O          0.87107       -3.81659        1.10926
60
Fig.3, L=PtBu3, Step 8, C21H40OPPd, Electronic Energy: -1365.431776 a.u. Gibbs Free Energy: -1364.970776 a.u., Corrected Gibbs Free Energy: -1364.967772 a.u.
P          1.37921        0.44455        0.00198
C          0.64703        2.05176        0.73112
C          2.63739       -0.29837        1.25741
C          2.21130        0.77198       -1.68988
C          0.30534        1.82298        2.20583
H         -0.29246        2.68452        2.55791
H          1.19433        1.76865        2.85302
H         -0.30659        0.91627        2.36433
C         -0.67069        2.40029        0.03462
H         -1.03669        3.36106        0.44474
H         -1.44432        1.63951        0.23976
H         -0.58959        2.52286       -1.05668
C          1.61533        3.23178        0.61823
H          1.18355        4.09056        1.16609
H          1.76993        3.56283       -0.42126
H          2.60328        3.02997        1.06153
C          1.35516        1.71604       -2.53758
H          1.81124        1.77094       -3.54359
H          1.31379        2.74597       -2.14998
H          0.32272        1.34904       -2.67826
C          3.61554        1.36627       -1.57518
H          3.97884        1.60096       -2.59322
H          4.28755        1.14926        0.94176
H          3.64033        2.30545       -0.99752
C          2.27210       -0.55859       -2.44999
H          2.73000       -0.37688       -3.44076
H          1.26042       -0.97252       -2.62253
H          2.87495       -1.33240       -1.95141
C          3.68802        0.70100        1.74890
H          4.34337        0.66618       -1.13467
H          4.38871        0.15734        2.41120
H          3.25260        1.51317        2.35287
C          3.36210       -1.46221        0.57472
H          4.05580       -1.13053       -0.21422
H          2.67382       -2.20763        0.13604
H          3.97075       -1.98811        1.33300
C          1.88445       -0.84394        2.48873
H          2.38593       -1.75900        2.85296
H          0.82995       -1.10556        2.29952
H          1.88582       -0.12754        3.32449
Pd        -0.30597       -1.15235       -0.38149
C         -2.52403       -1.16866       -1.34644
C         -2.16586       -2.45232       -1.01022
H         -0.49831        0.19380       -1.22876
H         -2.35400       -0.84525       -2.38220
H         -2.51367       -2.92446       -0.08219
H         -1.73165       -3.11694       -1.76695
C         -3.88449        0.88732       -1.11776
C         -3.29821       -0.23704       -0.51450
C         -3.44291       -0.41048        0.87417
C         -4.15747        0.51327        1.63105
C         -4.74326        1.62493        1.01704
C         -4.60693        1.80745       -0.35987
H         -3.76343        1.03935       -2.19758
H         -2.96776       -1.26701        1.36973
H         -4.25498        0.36980        2.71336
H         -5.30240        2.35263        1.61646
H         -5.06041        2.67825       -0.84721
C          0.15840       -2.77816        0.64715
O          0.39941       -3.76080        1.17794
44
Fig.3, L=PtBu3, Step 9, C13H31OPPd, Electronic Energy: -1056.038776  a.u.,Gibbs Free Energy: -1055.704875 a.u., Corrected Gibbs Free Energy: -1055.701763 a.u.
P         -0.63568       -0.03421        0.00885
C         -1.22169       -1.23847       -1.34974
C         -1.23898       -0.58273        1.73043
C         -1.18382        1.75999       -0.37596
C         -1.05465       -2.68037       -0.86671
H         -1.27714       -3.35174       -1.71673
H         -1.74567       -2.95566       -0.05450
H         -0.02002       -2.90081       -0.54619
C         -0.31113       -1.08798       -2.57462
H         -0.59425       -1.86123       -3.31345
H          0.75173       -1.24972       -2.31583
H         -0.39632       -0.11653       -3.08187
C         -2.67957       -1.01801       -1.75633
H         -2.96496       -1.80482       -2.47984
H         -2.84323       -0.05060       -2.25836
H         -3.37945       -1.08836       -0.90695
C         -0.89566        2.04943       -1.85096
H         -1.05371        3.12966       -2.02787
H         -1.56553        1.51411       -2.54173
H          0.15215        1.82473       -2.12450
C         -2.65528        2.03686       -0.07843
H         -2.89200        3.06562       -0.41200
H         -3.37411       -0.16393        1.36379
H         -3.34097        1.35664       -0.60971
C         -0.30951        2.73181        0.42964
H         -0.55461        3.76204        0.10998
H          0.77243        2.59576        0.23344
H         -0.46659        2.68844        1.51579
C         -2.71903       -0.96706        1.74059
H         -2.88735        1.98914        0.99836
H         -3.02191       -1.17169        2.78494
H         -2.92931       -1.88155        1.16212
C         -1.00882        0.55195        2.73119
H         -1.68728        1.40733        2.58554
H          0.03558        0.91406        2.72105
H         -1.20597        0.15854        3.74585
C         -0.38704       -1.75880        2.22052
H         -0.75330       -2.05592        3.22132
H          0.67407       -1.47092        2.32927
H         -0.43489       -2.65291        1.58275
Pd         1.71773        0.15370       -0.02172
C          3.65531       -0.09804        0.02649
O          4.76097       -0.37613        0.08325
H          1.49368       -1.36922        0.07940
89
Fig.3, L=PPh3, Step 1a (Thermolysis), C45H39ClOP2Pd, Electronic Energy: -3082.569037  a.u. Gibbs Free Energy: -3081.950676 a.u., Corrected Gibbs Free Energy: -3081.946286 a.u.
Pd        -0.11288       -0.92229       -0.14125
P          2.25998       -0.79983        0.08268
P         -0.75671        1.43271       -0.01232
Cl        -0.64286       -1.05373       -2.87521
C          0.12121        2.64836       -1.06484
C          3.07946       -2.21054       -0.74790
C         -2.50149        1.59189       -0.53827
C          3.19859        0.65590       -0.48922
C          2.74912       -0.98348        1.84299
C         -2.80164        1.73624       -1.90228
H         -1.99291        1.82513       -2.63716
C          4.02574        0.61082       -1.61949
H          4.15379       -0.32577       -2.17552
C          3.88806       -0.36774        2.38218
H          4.53577        0.25056        1.74980
C          0.06640        1.41967        2.63726
H          0.61254        0.51648        2.33509
C         -0.72326        2.08952        1.69207
C          0.70354        2.18680       -2.25548
H          0.62110        1.12173       -2.52055
C          1.95286       -1.78356        2.67757
H          1.04826       -2.25944        2.27528
C         -4.87996        1.47358       -0.05807
H         -5.69231        1.36577        0.67079
C          2.47883       -2.77822       -1.88021
H          1.51566       -2.38388       -2.24172
C         -3.55486        1.44686        0.37871
H         -3.34602        1.31927        1.44833
C         -5.17001        1.62805       -1.41371
H         -6.21183        1.64485       -1.75516
C          4.30961       -2.70977       -0.29486
H          4.79372       -2.27416        0.58847
C          4.70096        1.75767       -2.04259
H          5.34774        1.70920       -2.92635
C          4.32617       -4.32722       -2.09289
H          4.81267       -5.15842       -2.61669
C          0.21895        4.00701       -0.73436
H         -0.21416        4.38929        0.19695
C         -4.12723        1.75481       -2.33410
H         -4.34669        1.87258       -3.40175
C          3.41402       -1.33485        4.55016
H          3.66981       -1.46493        5.60807
C          3.10484       -3.83069       -2.55039
H          2.63004       -4.26850       -3.43630
C          1.35888        3.07687       -3.10662
H          1.80982        2.70637       -4.03518
C         -1.45017        3.22189        2.09561
H         -2.09633        3.74751        1.38179
C          3.04321        1.87202        0.19636
H          2.38013        1.92729        1.07154
C          4.56120        2.95521       -1.34143
H          5.09672        3.85280       -1.67243
C          4.92725       -3.76541       -0.96425
H          5.88598       -4.15280       -0.60036
C          4.21335       -0.53951        3.72871
H          5.10408       -0.04752        4.13626
C          3.72847        3.01014       -0.22017
H          3.60468        3.95047        0.32991
C          0.15470        1.88036        3.95115
H          0.77943        1.34319        4.67493
C          0.88169        4.89132       -1.58598
H          0.95445        5.95125       -1.31544
C          1.45062        4.42959       -2.77411
H          1.97263        5.12666       -3.44044
C          2.28558       -1.96301        4.01894
H          1.65156       -2.58995        4.65628
C         -1.36565        3.67959        3.40986
H         -1.93728        4.56429        3.71318
C         -0.56018        3.01423        4.33778
H         -0.49843        3.37827        5.36991
C         -0.36635       -2.76617       -0.00338
O         -0.37818       -3.92203       -0.08293
C         -3.14419       -1.94815       -0.49825
C         -2.13265       -1.77171        0.60141
H         -3.02384       -1.14107       -1.24652
H         -2.92758       -2.87580       -1.06566
H         -2.24162       -0.82957        1.16656
H         -2.14945       -2.58129        1.34917
C         -5.59720       -2.05890       -1.02679
C         -4.58817       -1.98643       -0.05223
C         -4.97512       -1.92542        1.29248
C         -6.32583       -1.93206        1.65329
C         -7.31621       -1.99761        0.67419
C         -6.94426       -2.06289       -0.67216
H         -5.31197       -2.10054       -2.08665
H         -4.21316       -1.86310        2.07894
H         -6.60365       -1.88189        2.71323
H         -8.37574       -1.99904        0.95632
H         -7.71331       -2.11431       -1.45269
89
Fig.3, L=PPh3, Step 1, C45H39ClOP2Pd, Electronic Energy:  -3082.625089 a.u. Gibbs Free Energy: -3082.013683 a.u., Corrected Gibbs Free Energy: -3082.004766 a.u.
Pd         0.06513       -0.82754       -0.16408
P         -2.29800       -0.94197       -0.01402
P          2.42278       -0.59350       -0.05298
Cl         0.24077       -2.98890        1.16240
O         -0.05115        0.76770       -2.49484
C          2.93029       -0.75414        1.69265
C         -3.03956       -2.33551       -0.92733
C          3.34082       -1.84498       -1.01113
C         -2.74460       -1.12869        1.74575
C         -3.27841        0.49169       -0.59472
C          4.72012       -1.72078       -1.24343
H          5.27217       -0.86411       -0.83585
C         -3.65425       -2.08071        2.21926
H         -4.16204       -2.75934        1.52348
C         -3.90383        1.39354        0.27648
H         -3.87667        1.22775        1.36011
C          3.68629        1.93636        0.28090
H          3.70343        1.73752        1.35928
C         -0.16810        2.12211       -0.52068
H          0.68602        2.16705        0.18538
H         -1.06425        2.05180        0.12867
C          3.17454        0.98147       -0.60804
C          4.01961       -1.52452        2.11418
H          4.63105       -2.06894        1.38446
C         -3.33171        0.73102       -1.97809
H         -2.84239        0.03763       -2.67402
C          3.32592       -3.89682       -2.30382
H          2.77586       -4.74583       -2.72568
C         -2.20218       -3.29869       -1.50632
H         -1.11492       -3.21204       -1.38028
C          2.64752       -2.93664       -1.55191
H          1.56800       -3.02986       -1.37426
C         -0.06135        0.82296       -1.28781
C          4.69813       -3.77212       -2.52336
H          5.22967       -4.52519       -3.11681
C         -4.42975       -2.43840       -1.09750
H         -5.09533       -1.68220       -0.66140
C         -3.91186       -2.18338        3.58837
H         -4.62110       -2.93683        3.95014
C         -4.13001       -4.45919       -2.39099
H         -4.55763       -5.28927       -2.96538
C          2.15312       -0.08186        2.64941
H          1.28452        0.50883        2.32434
C          5.39433       -2.68309       -1.99302
H          6.47158       -2.58023       -2.16765
C         -4.62468        2.73984       -1.60210
H         -5.15002        3.61820       -1.99488
C         -2.74744       -4.35722       -2.23435
H         -2.08536       -5.10436       -2.68685
C          4.32934       -1.61566        3.47320
H          5.18044       -2.22745        3.79409
C          3.16892        1.26464       -1.98428
H          2.76991        0.52894       -2.69416
C         -2.09285       -0.28664        2.66173
H         -1.36318        0.45050        2.29663
C         -3.26834       -1.33759        4.49165
H         -3.47105       -1.42413        5.56545
C         -4.97050       -3.49856       -1.82257
H         -6.05676       -3.57357       -1.94881
C         -4.57169        2.51172       -0.22705
H         -5.05786        3.20831        0.46600
C         -2.35828       -0.38514        4.02531
H         -1.84369        0.27861        4.72988
C          4.18598        3.14902       -0.19850
H          4.58596        3.88560        0.50815
C          2.47022       -0.16587        4.00298
H          1.85666        0.36469        4.74052
C          3.55944       -0.93691        4.41773
H          3.80412       -1.01340        5.48353
C         -0.37500        4.62707       -0.60546
C         -4.00429        1.84451       -2.47710
H         -4.04250        2.01544       -3.55928
C         -0.22575        3.36497       -1.40505
H          0.69682        3.40383       -2.01554
H         -1.06522        3.26274       -2.11616
C          3.67142        2.47444       -2.45866
H          3.66533        2.67928       -3.53562
C          4.17906        3.42218       -1.56627
H          4.57185        4.37490       -1.93986
C          0.69240        5.11477        0.16508
H          1.65054        4.57740        0.15468
C         -1.58651        5.33174       -0.57862
H         -2.43088        4.96953       -1.17952
C         -1.72927        6.48867        0.19042
H         -2.68513        7.02646        0.19250
C          0.55457        6.26957        0.93448
H          1.40331        6.63531        1.52505
C         -0.65922        6.96157        0.95117
H         -0.76861        7.87049        1.55460
94
Fig.3, L=PPh3, Step 2, C47H45NOP2Pd, Electronic Energy: -2755.033241 a.u. Gibbs Free Energy: -2754.373531 a.u., Corrected Gibbs Free Energy: -2754.366730 a.u.
Pd        -0.21002       -0.62145       -0.34935
P         -2.48748        0.06293       -0.15844
P          2.10261       -1.22353       -0.20643
O          0.20904        1.10549       -2.51859
C          2.30517       -1.88749        1.48038
C         -3.58516       -0.78767       -1.33383
C          2.54926       -2.56424       -1.35346
C         -3.02145       -0.42812        1.51546
C         -2.89928        1.83077       -0.33149
C          3.88641       -2.93052       -1.57231
H          4.69502       -2.39788       -1.05549
C         -4.18000       -1.17567        1.75868
H         -4.84960       -1.44682        0.93366
C         -3.15975        2.65450        0.77169
H         -3.20308        2.23192        1.78261
C          4.23199        0.45770        0.63164
H          4.12006        0.02787        1.63410
C          0.60208        2.23915       -0.43666
H          1.41981        1.91266        0.23742
H         -0.25540        2.43177        0.23987
C          3.41832        0.02157       -0.42256
C          2.81799       -3.16324        1.74279
H          3.19300       -3.79028        0.92490
C         -2.85149        2.39805       -1.61596
H         -2.64693        1.76775       -2.49092
C          1.83573       -4.29748       -2.89264
H          1.03122       -4.82712       -3.41517
C         -3.09633       -1.90038       -2.03284
H         -2.05712       -2.22362       -1.87875
C          1.52685       -3.25051       -2.02370
H          0.48064       -2.95213       -1.86757
C          0.23707        1.06612       -1.31367
C          3.16673       -4.66029       -3.10177
H          3.41009       -5.47958       -3.78809
C         -4.90584       -0.36239       -1.54714
H         -5.29804        0.50922       -1.00760
C         -4.48390       -1.59375        3.05621
H         -5.39037       -2.18307        3.23617
C         -5.23269       -2.16005       -3.13166
H         -5.87811       -2.69469       -3.83816
C          1.81558       -1.11001        2.54338
H          1.39253       -0.11531        2.34198
C          4.19082       -3.97546       -2.44273
H          5.23685       -4.25748       -2.60876
C         -3.32367        4.57988       -0.68603
H         -3.48834        5.65476       -0.82391
C         -3.91977       -2.58562       -2.92675
H         -3.52968       -3.45244       -3.47199
C          2.84159       -3.65287        3.05090
H          3.23940       -4.65548        3.24587
C          3.58407        0.58721       -1.69801
H          2.95551        0.25382       -2.53410
C         -2.16927       -0.11116        2.58666
H         -1.24369        0.45180        2.39786
C         -3.63955       -1.26613        4.11701
H         -3.88059       -1.59808        5.13346
C         -5.72415       -1.04836       -2.44262
H         -6.75463       -0.71214       -2.60478
C         -3.36901        4.02300        0.59209
H         -3.57483        4.65684        1.46233
C         -2.48193       -0.51956        3.88104
H         -1.81354       -0.26194        4.71067
C          5.20158        1.43764        0.40996
H          5.83613        1.76731        1.24075
C          1.84985       -1.59774        3.84745
H          1.46772       -0.98174        4.66966
C          2.35921       -2.87415        4.10262
H          2.37548       -3.26372        5.12703
C          1.38943        4.61370       -0.28505
C         -3.06741        3.76336       -1.79020
H         -3.03311        4.19316       -2.79799
C          0.99030        3.49810       -1.20753
H          1.82544        3.24899       -1.88941
H          0.14468        3.80940       -1.84658
C          4.55461        1.56328       -1.91383
H          4.67816        1.99331       -2.91450
C          5.36569        1.99110       -0.85975
H          6.12730        2.76076       -1.02993
C          2.62032        4.56692        0.38784
H          3.29845        3.72187        0.20517
C          0.53966        5.70065       -0.03933
H         -0.42500        5.75709       -0.56046
C          0.90866        6.71327        0.84900
H          0.23072        7.55749        1.02358
C          2.99301        5.57565        1.27516
H          3.96192        5.52175        1.78629
C          2.13619        6.65407        1.51038
H          2.42754        7.44940        2.20661
C         -1.17422       -4.48144        2.35416
H         -2.17400       -4.91264        2.17983
H         -0.41787       -5.27533        2.23707
H         -1.12832       -4.09598        3.38692
N         -0.71508       -2.53904        0.69164
C         -0.92304       -3.41413        1.42548
88
Fig.3, L=PPh3, Step 3, C45H39OP2Pd, Electronic Energy:   -2622.356886 a.u. Gibbs Free Energy: -2621.737603 a.u., Corrected Gibbs Free Energy: -2621.731401 a.u.
Pd        -0.10990       -0.51290       -0.91389
P          2.17666       -1.13632       -0.12059
P         -0.47504        1.54236        0.04106
O         -1.97665       -0.06398       -2.93515
C         -0.03043        1.41231        1.80621
C          3.40837        0.13918        0.30706
C          0.58654        2.81610       -0.71673
C          2.09053       -2.25368        1.31937
C          2.98032       -2.11790       -1.43657
C          0.39701        4.17863       -0.43015
H         -0.41411        4.49607        0.23687
C          3.11777       -2.40800        2.26096
H          4.04676       -1.83236        2.16527
C          4.08637       -2.94360       -1.18617
H          4.49265       -3.02741       -0.16965
C         -2.97064        2.25691        1.15658
H         -2.59807        1.86020        2.10878
C         -3.03208       -0.96099       -0.95655
H         -3.14147       -0.33565       -0.04864
H         -2.69152       -1.94651       -0.57934
C         -2.14391        2.27530        0.02443
C          0.50917        2.48181        2.53383
H          0.69010        3.45022        2.05280
C          2.47450       -2.02215       -2.74077
H          1.60694       -1.37548       -2.94324
C          2.44099        3.39816       -2.16869
H          3.23499        3.08915       -2.85842
C          3.32375        0.80385        1.54143
H          2.59870        0.47347        2.29638
C          1.60535        2.43577       -1.60146
H          1.73615        1.37434       -1.85508
C         -1.91072       -0.38363       -1.77929
C          2.26188        4.74700       -1.86174
H          2.91791        5.50325       -2.30800
C          4.35635        0.56962       -0.63338
H          4.43475        0.06993       -1.60720
C          2.96212       -3.29430        3.32750
H          3.76845       -3.40646        4.06153
C          5.10217        2.30501        0.87911
H          5.76176        3.15164        1.10181
C         -0.24251        0.18147        2.44515
H         -0.66366       -0.65906        1.87488
C          1.23616        5.13596       -0.99682
H          1.08381        6.19609       -0.76448
C          4.16861       -3.55545       -3.52534
H          4.63484       -4.11961       -4.34138
C          4.16539        1.87922        1.82328
H          4.08875        2.38669        2.79236
C          0.84067        2.31400        3.87816
H          1.27175        3.15232        4.43745
C         -2.64468        2.78308       -1.18593
H         -2.01038        2.80068       -2.08160
C          0.91070       -3.00060        1.46294
H          0.09572       -2.86738        0.73440
C          1.78777       -4.03815        3.45893
H          1.67020       -4.73260        4.29888
C          5.19902        1.64350       -0.34582
H          5.93506        1.96851       -1.09049
C          4.67583       -3.65873       -2.22692
H          5.53954       -4.30244       -2.02408
C          0.76190       -3.89419        2.52217
H         -0.16325       -4.47301        2.62357
C         -4.27569        2.74511        1.07889
H         -4.91287        2.72974        1.97063
C          0.08688        0.01820        3.79021
H         -0.08010       -0.94873        4.27927
C          0.63552        1.08386        4.50625
H          0.90522        0.95520        5.56083
C         -5.44224       -1.63112       -0.84574
C          3.06867       -2.73698       -3.78251
H          2.66782       -2.65474       -4.79918
C         -4.35163       -1.08025       -1.71774
H         -4.63017       -0.08092       -2.09886
H         -4.19853       -1.72750       -2.59970
C         -3.94769        3.27043       -1.25693
H         -4.32640        3.66996       -2.20463
C         -4.76682        3.25086       -0.12510
H         -5.79267        3.63243       -0.18335
C         -6.25168       -0.77651       -0.08338
H         -6.10886        0.30927       -0.16297
C         -5.64366       -3.01452       -0.73389
H         -5.01871       -3.69697       -1.32503
C         -6.62793       -3.52974        0.11010
H         -6.77405       -4.61446        0.17879
C         -7.23718       -1.28767        0.76193
H         -7.86409       -0.60235        1.34499
C         -7.42835       -2.66721        0.86220
H         -8.20370       -3.07045        1.52427
88
Fig.3, L=PPh3, Step 4, C45H42OP2Pd, Electronic Energy: -2622.333609 a.u. Gibbs Free Energy: -2621.713735 a.u., Corrected Gibbs Free Energy: -2621.708962 a.u.
Pd        -0.03969       -0.92633        0.50046
P          2.27228       -0.70389        0.02799
P         -0.92852        1.30792        0.00632
C         -0.48284        1.92408       -1.65026
C          2.91850       -2.30067       -0.57485
C         -2.75576        1.35579        0.01897
C          2.89270        0.51054       -1.18087
C          3.17635       -0.36214        1.57623
C         -3.49791        1.29183       -1.16914
H         -2.98721        1.26858       -2.13994
C          3.51197        0.11844       -2.37562
H          3.67199       -0.94294       -2.59796
C          4.30994        0.46043        1.62712
H          4.69966        0.92608        0.71422
C          0.60228        2.25857        2.12073
H          1.10644        1.28588        2.04549
C         -0.45260        2.55856        1.24675
C         -0.07569        0.98056       -2.60407
H         -0.00091       -0.08047       -2.32112
C          2.70223       -0.95327        2.75856
H          1.80747       -1.59072        2.72875
C         -4.82843        1.35468        1.28523
H         -5.34620        1.37652        2.25137
C          2.12577       -3.06472       -1.44326
H          1.11488       -2.72022       -1.70603
C         -3.43495        1.37513        1.24898
H         -2.86961        1.41894        2.18925
C         -5.56082        1.30215        0.09753
H         -6.65666        1.28546        0.12726
C          4.20071       -2.75156       -0.23455
H          4.83378       -2.16234        0.44057
C          3.93419        1.07984       -3.29573
H          4.41859        0.76116       -4.22585
C          3.88812       -4.70763       -1.62369
H          4.26707       -5.65209       -2.03084
C         -0.55639        3.27704       -2.00722
H         -0.87215        4.02980       -1.27518
C         -4.89266        1.26761       -1.12686
H         -5.46162        1.22290       -2.06299
C          4.47888        0.09834        4.01446
H          4.98622        0.28336        4.96828
C          2.61131       -4.26054       -1.96988
H          1.98572       -4.85038       -2.64938
C          0.25441        1.38350       -3.89776
H          0.57805        0.63960       -4.63502
C         -1.12140        3.78624        1.37885
H         -1.97399        4.02457        0.73110
C          2.69902        1.87764       -0.92656
H          2.20534        2.20101       -0.00017
C          3.74411        2.43608       -3.03294
H          4.07581        3.18878       -3.75760
C          4.67930       -3.95441       -0.75489
H          5.68048       -4.30460       -0.47876
C          4.95438        0.68990        2.84378
H          5.83898        1.33628        2.87342
C          3.12706        2.83347       -1.84375
H          2.97146        3.89759       -1.63098
C          1.00644        3.17756        3.08911
H          1.83271        2.92812        3.76537
C         -0.21910        3.67835       -3.29936
H         -0.27264        4.73930       -3.56939
C          0.18610        2.73390       -4.24497
H          0.45443        3.05339       -5.25878
C          3.35352       -0.72794        3.96932
H          2.97455       -1.19464        4.88553
C         -0.71634        4.70337        2.34737
H         -1.24254        5.66013        2.44172
C          0.34985        4.40369        3.19926
H          0.66223        5.12730        3.96095
C         -0.14946       -2.74002        0.96252
O         -0.00019       -3.87159        1.15979
C         -2.74410       -2.25120       -0.19355
C         -2.00305       -1.91919        1.07996
H         -2.45353       -1.54748       -0.99847
H         -2.41771       -3.24501       -0.56260
H         -2.27690       -0.94511        1.52305
H         -2.14122       -2.66079        1.88183
C         -5.02146       -2.24759       -1.25429
C         -4.25131       -2.24396       -0.08013
C         -4.92145       -2.23395        1.14954
C         -6.31793       -2.22985        1.20519
C         -7.06986       -2.23557        0.03097
C         -6.41373       -2.24522       -1.20303
H         -4.51157       -2.24518       -2.22695
H         -4.35077       -2.22189        2.08608
H         -6.82087       -2.21930        2.17982
H         -8.16541       -2.22993        0.07490
H         -6.99331       -2.24538       -2.13421
88
Fig.3, L=PPh3, Step 5, C45H42OP2Pd, Electronic Energy:  -2622.350046 a.u. Gibbs Free Energy: -2621.728786 a.u., Corrected Gibbs Free Energy: -2621.723914 a.u.
Pd        -0.17330        1.04385       -0.70354
P         -0.93010       -1.10944        0.07533
C         -0.19786       -2.43961       -0.92846
C         -0.44888       -1.23419        1.83081
C         -0.12403       -2.42889        2.48581
H         -0.07354       -3.37587        1.93806
C         -3.32969       -1.84829       -1.14217
H         -2.72700       -1.96016       -2.05279
C         -2.71722       -1.48369        0.06875
C          0.55633       -2.08230       -2.05577
H          0.68151       -1.02126       -2.31375
C         -0.20880       -0.03425        3.93058
H         -0.23943        0.90763        4.49038
C         -0.48008       -0.03609        2.56311
H         -0.72503        0.90669        2.05273
C          0.10683       -1.22938        4.57819
H          0.32568       -1.23151        5.65227
C         -0.40249       -3.79960       -0.64401
H         -1.04719       -4.10351        0.18881
C          0.15544       -2.42090        3.85295
H          0.41869       -3.35954        4.35437
C          1.14634       -3.06168       -2.85420
H          1.73848       -2.76743       -3.72898
C         -3.50500       -1.34539        1.22027
H         -3.04750       -1.05888        2.17517
C         -4.70405       -2.07223       -1.19596
H         -5.17020       -2.35629       -2.14645
C          0.19790       -4.77602       -1.43698
H          0.04385       -5.83511       -1.20115
C          0.98145       -4.40945       -2.53453
H          1.45023       -5.18242       -3.15429
C         -4.88082       -1.57165        1.16047
H         -5.48631       -1.46232        2.06771
C         -5.48295       -1.93158       -0.04534
H         -6.56479       -2.10339       -0.08971
C          0.20407        2.84640       -1.26260
O          0.38670        3.93121       -1.57303
C         -2.98225        1.90462       -0.05894
C         -2.18352        1.45420       -1.26149
H         -2.73755        1.29189        0.83208
H         -2.67196        2.93126        0.22540
H         -2.55310        0.51015       -1.69603
H         -2.18405        2.21128       -2.06498
C         -5.30666        2.03274        0.90226
C         -4.48596        1.87397       -0.22678
C         -5.10516        1.67252       -1.46698
C         -6.49801        1.63027       -1.57718
C         -7.29923        1.78764       -0.44689
C         -6.69553        1.99194        0.79720
H         -4.83896        2.18213        1.88490
H         -4.49379        1.54279       -2.36833
H         -6.95924        1.46980       -2.55938
H         -8.39171        1.75106       -0.53255
H         -7.31397        2.11507        1.69472
P          2.21831        0.62190       -0.11541
C          3.21453        0.43789       -1.63751
C          2.84146        2.12048        0.73034
C          2.78879       -0.74289        0.95957
C          4.19474        2.48603        0.69979
H          4.91840        1.88928        0.13085
C          3.03756       -0.53059        2.32369
H          2.92666        0.47019        2.75877
C          2.93941       -2.03628        0.43279
H          2.76757       -2.22232       -0.63370
C          2.66382        0.84422       -2.86280
H          1.64114        1.24394       -2.89776
C          4.51169       -0.09988       -1.62007
H          4.96037       -0.43154       -0.67604
C          4.63113        3.61534        1.39130
H          5.68955        3.89751        1.35514
C          4.68400        0.19033       -4.01596
H          5.25725        0.08907       -4.94465
C          3.58917       -2.87070        2.60784
H          3.90509       -3.69993        3.25144
C          3.39535        0.72465       -4.04411
H          2.95009        1.04319       -4.99336
C          1.93722        2.89867        1.46793
H          0.87364        2.62167        1.49511
C          3.72551        4.38361        2.12629
H          4.07262        5.27071        2.66848
C          5.23967       -0.22107       -2.80296
H          6.25103       -0.64239       -2.77528
C          3.43880       -1.58918        3.13908
H          3.63394       -1.40687        4.20243
C          2.37827        4.02322        2.16615
H          1.66274        4.62286        2.74005
C          3.33759       -3.09106        1.25244
H          3.45839       -4.09284        0.82315
88
Fig.3, L=PPh3, Step 6, C45H42OP2Pd, Electronic Energy:  -2622.305555 a.u. Gibbs Free Energy: -2621.693391 a.u., Corrected Gibbs Free Energy: -2621.688478 a.u.
Pd        -0.07504       -0.51868       -1.15049
P         -1.74546        0.77772       -0.05886
C         -3.17263        1.19522       -1.13633
C         -2.51645       -0.12906        1.33019
C         -3.10540        0.52280        2.42374
H         -3.08769        1.61689        2.49430
C         -1.40546        3.56108       -0.15246
H         -1.90151        3.51613       -1.12994
C         -1.24977        2.39661        0.61620
C         -3.22966        0.79004       -2.47492
H         -2.39997        0.22171       -2.91280
C         -3.18964       -2.26579        2.26728
H         -3.22042       -3.35947        2.20287
C         -2.56322       -1.52944        1.26263
H         -2.08981       -2.04748        0.41571
C         -3.76566       -1.61024        3.35713
H         -4.25003       -2.18829        4.15253
C         -4.24191        1.93221       -0.60036
H         -4.21442        2.26708        0.44461
C         -3.72105       -0.21722        3.43338
H         -4.17316        0.30242        4.28591
C         -4.33686        1.11001       -3.26422
H         -4.36734        0.78745       -4.31113
C         -0.59341        2.47827        1.85428
H         -0.47503        1.58289        2.47629
C         -0.91983        4.78239        0.31361
H         -1.05030        5.68462       -0.29517
C         -5.34621        2.24772       -1.38809
H         -6.17553        2.81922       -0.95588
C         -5.39592        1.83662       -2.72273
H         -6.26537        2.08625       -3.34182
C         -0.10534        3.70106        2.31374
H          0.40068        3.75044        3.28524
C         -0.26626        4.85523        1.54486
H          0.11715        5.81573        1.90808
C         -0.34182       -2.56286       -2.24980
C          0.94729       -2.00934       -2.36361
H         -1.39724       -1.23961       -1.75171
H          1.77468       -2.43797       -1.78623
H          1.23204       -1.52187       -3.30506
C         -1.87376       -4.33732       -1.41366
C         -0.69489       -3.59452       -1.25112
C          0.11142       -3.84534       -0.12759
C         -0.25214       -4.81404        0.80340
C         -1.42551       -5.55372        0.62690
C         -2.23397       -5.31343       -0.48511
H         -2.51515       -4.14116       -2.28189
H          1.03118       -3.26728        0.02974
H          0.38526       -4.99288        1.67754
H         -1.71133       -6.31534        1.36154
H         -3.15639       -5.88761       -0.62944
H         -0.99724       -2.52426       -3.13124
P          1.95474        0.14110        0.00972
C          1.64564       -0.03203        1.80259
C          3.35399       -0.99047       -0.32066
C          2.70506        1.79074       -0.21933
C          3.68804       -2.03845        0.54528
H          3.15620       -2.16379        1.49651
C          4.04357        2.03643        0.13127
H          4.66588        1.22915        0.53701
C          1.93542        2.83662       -0.74210
H          0.89221        2.65453       -1.02561
C          0.70730       -0.99253        2.20726
H          0.19615       -1.60053        1.44735
C          2.28369        0.75297        2.77193
H          3.01193        1.51863        2.47827
C          4.70314       -2.93578        0.20438
H          4.95733       -3.75105        0.89148
C          1.04096       -0.37597        4.51745
H          0.80122       -0.50307        5.57948
C          3.81118        4.34659       -0.54971
H          4.24572        5.34434       -0.68078
C          0.41033       -1.17017        3.55773
H         -0.32475       -1.92616        3.85949
C          4.04676       -0.85719       -1.53518
H          3.78328       -0.05011       -2.23258
C          5.39307       -2.79265       -0.99867
H          6.19115       -3.49597       -1.26261
C          1.97696        0.58231        4.12228
H          2.47208        1.20891        4.87315
C          4.58924        3.30831       -0.03134
H          5.63366        3.48960        0.24729
C          5.06356       -1.74872       -1.86768
H          5.60064       -1.63050       -2.81581
C          2.48397        4.10926       -0.90615
H          1.86845        4.91654       -1.32011
C          0.10014        1.29631       -2.99797
O          0.88807        1.22422       -3.82090
88
Fig.3, L=PPh3, Step 7, C45H42OP2Pd, Electronic Energy:  -2622.308978 a.u. Gibbs Free Energy: -2621.695955 a.u., Corrected Gibbs Free Energy: -2621.691206 a.u.
Pd         0.08460        0.47303       -1.21620
P          1.92759       -0.38627       -0.06958
C          3.44262       -0.66458       -1.06780
C          2.45963        0.79584        1.22124
C          3.13149        0.37549        2.37926
H          3.31968       -0.68960        2.55842
C          2.09233       -3.17823        0.14599
H          2.58828       -3.15102       -0.83203
C          1.70580       -1.98569        0.77815
C          3.50935       -0.37222       -2.43463
H          2.63115        0.02516       -2.95704
C          2.67995        3.09950        1.95582
H          2.50129        4.16738        1.78532
C          2.23642        2.16616        1.01983
H          1.70015        2.50457        0.12204
C          3.34200        2.67327        3.10861
H          3.68416        3.40582        3.84862
C          4.58124       -1.17910       -0.42451
H          4.55060       -1.42389        0.64491
C          3.56480        1.31155        3.31815
H          4.08410        0.97040        4.22095
C          4.69157       -0.58592       -3.14680
H          4.72702       -0.35518       -4.21747
C          1.04994       -2.05029        2.01733
H          0.75616       -1.13051        2.53599
C          1.83451       -4.40878        0.74804
H          2.14343       -5.33230        0.24488
C          5.76070       -1.38587       -1.13518
H          6.64245       -1.78156       -0.61849
C          5.81797       -1.09066       -2.49958
H          6.74594       -1.25688       -3.05874
C          0.78751       -3.28425        2.61154
H          0.27855       -3.31896        3.58202
C          1.17845       -4.46550        1.97889
H          0.97299       -5.43447        2.44843
C         -0.36706        2.49608       -2.42781
C         -1.39808        1.59481       -2.58392
H          1.42541        1.12742       -1.77778
H         -2.33167        1.70837       -2.02268
H         -1.44235        0.96574       -3.48123
C          0.67333        4.55678       -1.52297
C         -0.31200        3.56061       -1.41887
C         -1.20691        3.60916       -0.33466
C         -1.11780        4.62306        0.61374
C         -0.13889        5.61453        0.49294
C          0.75478        5.57918       -0.57930
H          1.38409        4.52060       -2.35804
H         -1.96936        2.82717       -0.22262
H         -1.81664        4.63889        1.45887
H         -0.06990        6.41283        1.24101
H          1.52701        6.35096       -0.67710
H          0.41058        2.54011       -3.20103
P         -1.84422       -0.49371        0.00323
C         -1.63079       -0.08575        1.77436
C         -3.49121        0.19721       -0.40372
C         -2.16884       -2.29233       -0.08187
C         -4.10865        1.17940        0.38017
H         -3.63731        1.52528        1.30852
C         -3.39012       -2.83753        0.35146
H         -4.17699       -2.18500        0.74935
C         -1.19544       -3.14738       -0.60962
H         -0.24572       -2.73056       -0.96228
C         -0.88904        1.06229        2.08544
H         -0.45305        1.66013        1.27332
C         -2.16293       -0.85699        2.81640
H         -2.73609       -1.76651        2.60096
C         -5.33147        1.72825       -0.01414
H         -5.80642        2.49451        0.60935
C         -1.21072        0.66284        4.44444
H         -1.04438        0.94958        5.48926
C         -2.63045       -5.05571       -0.24719
H         -2.81347       -6.13446       -0.31314
C         -0.68584        1.44168        3.41194
H         -0.10721        2.34593        3.63739
C         -4.11323       -0.22232       -1.59157
H         -3.63010       -0.97794       -2.22683
C         -5.94722        1.30107       -1.18982
H         -6.90767        1.73140       -1.49591
C         -1.94767       -0.48513        4.14351
H         -2.35887       -1.10122        4.95153
C         -3.61379       -4.21061        0.27382
H         -4.56877       -4.62418        0.61778
C         -5.33507        0.32234       -1.97804
H         -5.81228       -0.01667       -2.90474
C         -1.42178       -4.52194       -0.69247
H         -0.64817       -5.17544       -1.11248
C          0.36196       -1.54357       -3.02839
O         -0.46085       -1.63621       -3.81223
72
Fig.3, L=PPh3, Step 8, C37H34OP2Pd, Electronic Energy: -2312.942985 a.u.
 Gibbs Free Energy: -2312.457568 a.u., Corrected Gibbs Free Energy: -2312.450993 a.u.
Pd        -0.01272       -0.22690       -0.45086
P         -2.32385        0.03500       -0.08425
P          2.29552        0.07605       -0.09557
C          2.69306       -0.20149        1.66140
C         -3.41750       -1.16885       -0.90968
C          3.39421       -1.05340       -1.01227
C         -2.51301       -0.24073        1.70434
C         -3.05439        1.65813       -0.46011
C          4.29815       -0.59854       -1.98052
H          4.39178        0.47261       -2.19516
C         -2.15259       -1.49920        2.21497
H         -1.84631       -2.30299        1.53133
C         -4.44552        1.82976       -0.36993
H         -5.08859        0.98856       -0.08055
C          3.98737        2.33360        0.04428
H          4.56290        1.79349        0.80646
C          2.84971        1.75259       -0.53122
C          3.98079       -0.59508        2.05934
H          4.76644       -0.75620        1.31079
C         -2.24800        2.73962       -0.83653
H         -1.16203        2.60804       -0.92244
C          4.08438       -3.33584       -1.45438
H          3.99853       -4.40817       -1.24507
C         -3.22411       -1.39649       -2.28099
H         -2.41461       -0.87861       -2.81400
C          3.28739       -2.43079       -0.75899
H          2.57522       -2.79852       -0.00707
C          4.98792       -2.87719       -2.41734
H          5.61289       -3.59063       -2.96657
C         -4.45046       -1.83704       -0.23805
H         -4.61905       -1.66617        0.83199
C         -2.17842       -1.73154        3.58760
H         -1.90175       -2.71784        3.97713
C         -5.07754       -2.94616       -2.29589
H         -5.72526       -3.64570       -2.83661
C          1.69915       -0.01346        2.63417
H          0.68483        0.27782        2.32927
C          5.09095       -1.51172       -2.67926
H          5.79720       -1.14709       -3.43383
C         -4.20445        4.14909       -1.00843
H         -4.65562        5.12457       -1.22353
C         -4.05331       -2.27809       -2.97081
H         -3.89464       -2.44922       -4.04153
C          4.26898       -0.78279        3.41022
H          5.27747       -1.08779        3.71172
C          2.12651        2.45684       -1.50372
H          1.22946        2.00170       -1.94711
C         -2.87924        0.78339        2.58572
H         -3.15018        1.77499        2.20350
C         -2.54809       -0.70762        4.46412
H         -2.56271       -0.88968        5.54483
C         -5.27378       -2.72465       -0.93242
H         -6.07720       -3.24621       -0.39991
C         -5.01457        3.07216       -0.63907
H         -6.10008        3.20065       -0.56110
C         -2.89463        0.54663        3.96199
H         -3.18298        1.35320        4.64561
C          4.39265        3.60814       -0.35095
H          5.27907        4.06149        0.10699
C          1.99376       -0.20170        3.98422
H          1.21178       -0.05218        4.73741
C          3.27764       -0.58592        4.37348
H          3.50638       -0.73887        5.43443
C         -2.82357        3.98152       -1.10856
H         -2.18583        4.82218       -1.40427
C          2.54045        3.72713       -1.90253
H          1.97119        4.27198       -2.66417
C          3.67245        4.30410       -1.32405
H          3.99383        5.30621       -1.63041
C         -0.01639       -1.95656       -1.40665
O         -0.02633       -2.96145       -1.94763
H         -0.00722        1.17471        0.33868
73
Fig.3, L=dppe, Step 1a (Thermolysis), C35H33ClOP2Pd, Electronic Energy:  -2698.221626 a.u. Gibbs Free Energy:  -2697.721871 a.u., Corrected Gibbs Free Energy: -2697.716342 a.u.
C          2.50558       -0.76452       -1.84613
C          1.66317       -1.85877       -1.21784
H          2.20643       -0.60237       -2.89795
H          2.32069        0.18856       -1.31423
H          1.77254       -2.83168       -1.72502
H          1.93058       -2.04375       -0.16058
C          4.71487       -1.42438       -2.91394
C          3.97260       -1.10068       -1.77118
C          4.62250       -1.11610       -0.52661
C          5.97649       -1.43122       -0.42821
C          6.70706       -1.74752       -1.57708
C          6.07124       -1.74486       -2.81930
H          4.22187       -1.41925       -3.89464
H          4.05124       -0.87236        0.37962
H          6.46681       -1.42904        0.55322
H          7.77238       -1.99603       -1.50263
H          6.63649       -1.99221       -3.72601
C         -0.17133       -1.80102       -1.93346
O         -0.35794       -2.06091       -3.05866
Pd        -0.21860       -1.10219       -0.21923
P         -2.31116       -0.31028        0.41629
P          0.44563        0.87538        1.13773
C          0.33542        2.41271        0.14900
C         -2.14736        0.27990        2.15199
C         -0.86747        1.07517        2.43946
C         -2.92221        1.09486       -0.57080
C         -3.69510       -1.49509        0.43667
C         -3.11765        2.37287       -0.03011
H         -2.95297        2.56123        1.03762
C         -3.51594       -2.79006       -0.06561
H         -2.53789       -3.08353       -0.47085
C          3.08509        1.79430        1.49320
H          2.91726        2.43214        0.61663
C          2.04443        0.99723        1.99871
C          0.36461        3.68106        0.74970
H          0.49386        3.77249        1.83633
C         -4.94787       -1.11592        0.94424
H         -5.10274       -0.09976        1.32946
C         -3.51500        3.42979       -0.85183
H         -3.65694        4.42731       -0.41928
C          0.18044        2.32168       -1.24095
H          0.14302        1.32999       -1.71588
C         -5.81627       -3.31949        0.45638
H         -6.64787       -4.03373        0.46457
C          0.23181        4.83213       -0.02535
H          0.25288        5.81769        0.45439
C          2.29762        0.17232        3.10896
H          1.50893       -0.49142        3.48413
C         -3.13309        0.89200       -1.94450
H         -2.97167       -0.10357       -2.38063
C         -3.72723        3.21978       -2.21430
H         -4.03751        4.05183       -2.85707
C         -4.57536       -3.69887       -0.05573
H         -4.42858       -4.71031       -0.45153
C         -3.53992        1.94608       -2.75889
H         -3.70575        1.77474       -3.82882
C          4.34208        1.78413        2.09877
H          5.14178        2.41627        1.69493
C          0.04960        3.47422       -2.01749
H         -0.07936        3.38844       -3.10297
C          0.07198        4.73011       -1.41009
H         -0.03648        5.63643       -2.01751
C         -6.00163       -2.02763        0.95582
H         -6.97710       -1.72672        1.35517
C          3.55553        0.16814        3.71001
H          3.73739       -0.47603        4.57845
C          4.58098        0.97447        3.20992
H          5.56857        0.96868        3.68577
H         -0.43432        0.74590        3.39948
H         -1.08099        2.15335        2.54813
H         -3.05188        0.84035        2.44973
H         -2.13803       -0.65783        2.73306
Cl        -0.02816       -2.38383        2.17693
73
Fig.3, L=dppe, Step 1, C35H33ClOP2Pd, Electronic Energy:  -2698.274981 a.u. Gibbs Free Energy: -2697.773427 a.u., Corrected Gibbs Free Energy: -2697.767059 a.u.
C         -3.97967       -0.27009       -1.82922
C         -2.67069       -0.60479       -1.11755
H         -4.19179        0.80721       -1.70446
H         -3.84524       -0.43990       -2.91355
H         -2.76768       -0.47798       -0.02013
H         -2.39880       -1.66966       -1.25535
C         -6.02853       -0.56148       -0.37622
C         -5.12604       -1.08901       -1.31072
C         -5.29359       -2.42310       -1.71330
C         -6.32940       -3.20391       -1.20071
C         -7.22000       -2.66492       -0.26897
C         -7.06616       -1.33943        0.14072
H         -5.91822        0.48250       -0.05494
H         -4.59766       -2.85291       -2.44612
H         -6.44457       -4.24278       -1.53306
H         -8.03536       -3.27723        0.13415
H         -7.76296       -0.90450        0.86765
Cl         0.50746       -1.96033       -2.46062
C         -1.49048        0.22322       -1.57290
O         -1.57047        1.07728       -2.42261
Pd         0.28487       -0.26910       -0.70239
P         -0.05081        1.31430        0.90165
P          2.43205       -0.64602        0.44384
C          3.95580       -0.29953       -0.49757
C          1.06461        0.92363        2.31804
C          2.46284        0.61883        1.80047
C          0.48562        2.96863        0.35076
C         -1.71333        1.55450        1.59645
C          0.45066        4.06938        1.22111
H          0.06148        3.95435        2.24126
C         -2.59895        2.44593        0.96865
H         -2.25550        3.06266        0.12786
C          3.15119       -3.33557        0.44758
H          3.34159       -3.18814       -0.62341
C          2.74390       -2.25176        1.24559
C          5.22767       -0.66283       -0.02929
H          5.33036       -1.21006        0.91675
C         -2.18133        0.75986        2.65409
H         -1.51794        0.04011        3.14760
C          0.90918        5.31392        0.79359
H          0.87962        6.16957        1.47813
C          3.84368        0.39929       -1.70812
H          2.84810        0.67679       -2.08195
C         -4.37608        1.76162        2.46006
H         -5.41644        1.84065        2.79643
C          6.36607       -0.32962       -0.76203
H          7.35635       -0.61687       -0.38952
C          2.50395       -2.46934        2.61051
H          2.18237       -1.64618        3.25930
C          0.98095        3.13388       -0.94940
H          0.99514        2.27303       -1.63196
C          1.40657        5.47057       -0.50322
H          1.76728        6.45086       -0.83591
C         -3.92004        2.54926        1.40093
H         -4.60016        3.25000        0.90260
C          1.44180        4.38135       -1.37395
H          1.82790        4.50201       -2.39264
C          3.32927       -4.59899        1.00686
H          3.65628       -5.43124        0.37263
C          4.98504        0.73518       -2.43753
H          4.88670        1.27954       -3.38378
C          6.24649        0.36989       -1.96565
H          7.14359        0.62865       -2.54019
C         -3.50409        0.86815        3.08381
H         -3.85530        0.24485        3.91422
C          2.67816       -3.73841        3.16575
H          2.49151       -3.89034        4.23528
C          3.09201       -4.80525        2.36820
H          3.23048       -5.80016        2.80691
H          3.14099        0.31075        2.61720
H          2.90798        1.52616        1.34970
H          1.07197        1.76643        3.03438
H          0.63989        0.04913        2.84324
78
Fig.3, L=dppe, Step 2, C37H39NOP2Pd, Electronic Energy:  -2370.677690 a.u. Gibbs Free Energy: -2370.135123 a.u., Corrected Gibbs Free Energy: -2370.127807 a.u.
C         -3.95197       -0.47959       -1.74252
C         -2.63511       -0.69786       -1.00107
H         -4.20653        0.59540       -1.71292
H         -3.80501       -0.73868       -2.80718
H         -2.73601       -0.47159        0.07920
H         -2.32613       -1.76252       -1.03512
C         -5.99974       -0.72352       -0.27804
C         -5.06829       -1.29498       -1.15643
C         -5.17803       -2.66500       -1.44026
C         -6.18642       -3.43908       -0.86669
C         -7.10694       -2.85621        0.00778
C         -7.01047       -1.49456        0.29910
H         -5.93429        0.34845       -0.04999
H         -4.45907       -3.12896       -2.12868
H         -6.25706       -4.50700       -1.10638
H         -7.90113       -3.46299        0.45861
H         -7.73136       -1.02588        0.97998
C         -1.47996        0.10824       -1.54287
O         -1.55399        0.81895       -2.51367
Pd         0.30932       -0.21934       -0.58921
P         -0.11670        1.55729        0.78465
P          2.42053       -0.39237        0.65060
C          3.96183       -0.24692       -0.30834
C          1.00233        1.40434        2.24216
C          2.41407        1.06781        1.78452
C          0.35629        3.13154        0.00214
C         -1.79800        1.80158        1.42461
C          0.18628        4.34863        0.68060
H         -0.26961        4.36582        1.67888
C         -2.72068        2.53840        0.66367
H         -2.39898        3.04217       -0.25717
C          2.96566       -3.08074        1.05020
H          3.11708       -3.10369       -0.03740
C          2.65542       -1.86780        1.69036
C          5.22112       -0.46398        0.27192
H          5.29794       -0.75533        1.32746
C         -2.23510        1.14990        2.58773
H         -1.54033        0.55395        3.19031
C          0.59388        5.54147        0.08704
H          0.45666        6.48903        0.62048
C          3.87867        0.11998       -1.65912
H          2.89294        0.28064       -2.11806
C         -4.47837        1.98412        2.22958
H         -5.52651        2.05297        2.54302
C          6.37780       -0.30995       -0.49032
H          7.35874       -0.47932       -0.03126
C          2.46353       -1.86160        3.07933
H          2.21965       -0.93253        3.60771
C          0.93868        3.12642       -1.27235
H          1.06235        2.17412       -1.80592
C          1.17613        5.52963       -1.18340
H          1.49519        6.47006       -1.64747
C         -4.05128        2.62994        1.06737
H         -4.76170        3.20839        0.46535
C          1.34913        4.32314       -1.86183
H          1.80265        4.31163       -2.85938
C          3.09671       -4.25541        1.78675
H          3.34821       -5.19171        1.27521
C          5.03926        0.27505       -2.41879
H          4.96612        0.56046       -3.47441
C          6.28815        0.06007       -1.83493
H          7.20004        0.17835       -2.43169
C         -3.56821        1.24603        2.98716
H         -3.89676        0.73637        3.90009
C          2.58993       -3.04325        3.81262
H          2.44186       -3.02308        4.89852
C          2.90705       -4.24030        3.17112
H          3.00739       -5.16543        3.75021
H          3.09195        0.91060        2.64317
H          2.83929        1.90457        1.19844
H          0.97780        2.34441        2.82431
H          0.59858        0.60576        2.89056
C          1.22521       -3.87811       -3.43765
H          2.07392       -3.61721       -4.09117
H          1.50254       -4.75423       -2.82834
H          0.35820       -4.14025       -4.06590
N          0.65050       -1.87433       -1.89089
C          0.90373       -2.76882       -2.58487
72
Fig.3, L=dppe, Step 3, C35H33OP2Pd, Electronic Energy:  -2238.004535 a.u. Gibbs Free Energy: -2237.501640 a.u., Corrected Gibbs Free Energy: -2237.494961 a.u.
C         -3.95361       -0.17733       -1.90633
C         -2.63733       -0.50669       -1.20507
H         -4.23756        0.86112       -1.65607
H         -3.79259       -0.20872       -2.99900
H         -2.74733       -0.47569       -0.10276
H         -2.31134       -1.54337       -1.42510
C         -5.89623       -0.84648       -0.43438
C         -5.04396       -1.13039       -1.51118
C         -5.20149       -2.35389       -2.17911
C         -6.18332       -3.26422       -1.78765
C         -7.02690       -2.96749       -0.71483
C         -6.88007       -1.75425       -0.03955
H         -5.78905        0.10827        0.09711
H         -4.54272       -2.59189       -3.02483
H         -6.29365       -4.21278       -2.32690
H         -7.80076       -3.68057       -0.40703
H         -7.54025       -1.51012        0.80147
C         -1.50065        0.41268       -1.57795
O         -1.57980        1.32130       -2.36278
Pd         0.28419       -0.20790       -0.83078
P          0.00406        1.27381        0.85438
P          2.43012       -0.80140        0.20404
C          3.98206       -0.56128       -0.72228
C          1.18187        0.75869        2.17320
C          2.54366        0.44054        1.57285
C          0.53801        2.94142        0.36179
C         -1.62745        1.47113        1.61699
C          0.43810        4.01519        1.26062
H         -0.00078        3.86502        2.25547
C         -2.53892        2.37755        1.04893
H         -2.22999        3.02404        0.21732
C          2.77283       -3.55248        0.14172
H          2.82534       -3.41232       -0.94625
C          2.61072       -2.43920        0.98464
C          5.21646       -1.01773       -0.23591
H          5.26506       -1.56739        0.71304
C         -2.04886        0.64206        2.66777
H         -1.36264       -0.08461        3.11708
C          0.89600        5.27802        0.89050
H          0.81508        6.11352        1.59520
C          3.93571        0.13627       -1.93767
H          2.96956        0.48600       -2.32725
C         -4.25354        1.63701        2.58474
H         -5.28020        1.70080        2.96315
C          6.38517       -0.77394       -0.95571
H          7.34655       -1.13254       -0.57006
C          2.53718       -2.64175        2.36976
H          2.40869       -1.79585        3.05446
C          1.09957        3.14869       -0.90492
H          1.16835        2.30728       -1.60806
C          1.45731        5.47836       -0.37348
H          1.81543        6.47365       -0.66100
C         -3.84235        2.45993        1.53384
H         -4.54345        3.17290        1.08496
C          1.55976        4.41449       -1.26999
H          1.99708        4.56986       -2.26270
C          2.87796       -4.83484        0.67469
H          3.01332       -5.69195        0.00494
C          5.10790        0.38149       -2.65410
H          5.06280        0.92610       -3.60412
C          6.33239       -0.07416       -2.16394
H          7.25324        0.11424       -2.72805
C         -3.35484        0.73078        3.14935
H         -3.67118        0.08313        3.97487
C          2.63413       -3.93030        2.89975
H          2.57834       -4.07336        3.98510
C          2.80711       -5.02758        2.05684
H          2.88614       -6.03711        2.47629
H          3.25786        0.11080        2.34916
H          2.98194        1.34703        1.11373
H          1.25049        1.56649        2.92625
H          0.75494       -0.12697        2.67750
72
Fig.3, L=dppe, Step 4, C35H33OP2Pd, Energy: -2237.982387 a.u. Gibbs Free Energy: -2237.477362 a.u., Corrected Gibbs Free Energy: -2237.472265 a.u.
Pd         0.33721       -0.28373       -0.83864
C         -2.23955       -2.12714       -1.07315
C         -1.53677       -1.05360       -1.88435
H         -1.90633       -3.12902       -1.40050
H         -1.96011       -2.03375       -0.00626
H         -1.63253       -1.19368       -2.97362
H         -1.92642       -0.04147       -1.67367
C         -4.46250       -2.84400       -2.06623
C         -3.73570       -2.01074       -1.20630
C         -4.42866       -1.02412       -0.48838
C         -5.80950       -0.88155       -0.61434
C         -6.52405       -1.72226       -1.47201
C         -5.84565       -2.70232       -2.19824
H         -3.93549       -3.62016       -2.63622
H         -3.86881       -0.35977        0.18479
H         -6.33260       -0.10956       -0.03632
H         -7.61035       -1.61347       -1.57304
H         -6.39873       -3.36709       -2.87272
C          0.37805       -1.68153       -2.10029
O          0.57605       -2.60375       -2.77530
P          2.40733        0.02652        0.19124
P         -0.42314        1.33509        0.80462
C         -1.87287        0.85509        1.79230
C          2.30439        1.51591        1.26665
C          0.96908        1.52757        1.99660
C          2.72393       -1.36304        1.33300
C          3.92148        0.18733       -0.79787
C          3.85496       -1.34739        2.16393
H          4.55980       -0.50692        2.12003
C          4.18856       -0.80439       -1.75567
H          3.48494       -1.63628       -1.89294
C         -1.76693        3.06966       -0.88471
H         -2.32193        2.17433       -1.19487
C         -0.77383        2.97484        0.10566
C         -2.97972        1.69153        1.99112
H         -2.99072        2.70600        1.57535
C          4.82189        1.24941       -0.63486
H          4.63544        2.03301        0.10795
C          4.08945       -2.40060        3.04549
H          4.97458       -2.38198        3.69157
C         -1.88158       -0.43983        2.33813
H         -1.02222       -1.10655        2.18266
C          6.23696        0.32278       -2.36634
H          7.14285        0.37723       -2.98085
C         -4.07670        1.23716        2.72515
H         -4.93736        1.89891        2.87615
C         -0.07470        4.12916        0.48448
H          0.70787        4.08498        1.25029
C          1.83922       -2.44834        1.39221
H          0.95708       -2.46919        0.73628
C          3.20128       -3.47794        3.10303
H          3.38945       -4.30573        3.79640
C          5.34295       -0.73830       -2.53153
H          5.54401       -1.51804       -3.27482
C          2.07812       -3.50164        2.27643
H          1.38179       -4.34689        2.31654
C         -2.06516        4.29795       -1.46931
H         -2.84792        4.35969       -2.23379
C         -2.97569       -0.88536        3.07678
H         -2.97082       -1.89651        3.49948
C         -4.07770       -0.04847        3.26761
H         -4.94240       -0.40191        3.84101
C          5.97433        1.31338       -1.42029
H          6.67350        2.14675       -1.28691
C         -0.36910        5.35590       -0.11315
H          0.18525        6.25124        0.19048
C         -1.36393        5.44395       -1.08649
H         -1.59355        6.40931       -1.55192
H          0.84393        2.43429        2.61460
H          0.89488        0.66688        2.68814
H          3.14922        1.53811        1.97929
H          2.40480        2.39996        0.60905
72
Fig.3, L=dppe, Step 5, C35H33OP2Pd, Electronic Energy: -2237.488593 a.u. Gibbs Free Energy: -2237.493170 a.u., Corrected Gibbs Free Energy: -2237.488593 a.u.
C          2.72260       -0.63242       -1.34491
C          1.82548       -1.63092       -0.63685
H          2.39217       -0.48465       -2.38967
H          2.65777        0.36190       -0.85749
H          1.86702       -2.61072       -1.14532
H          2.13786       -1.78548        0.41512
C          4.84773       -1.41386       -2.50608
C          4.16254       -1.08092       -1.33045
C          4.84533       -1.19125       -0.10892
C          6.17554       -1.60456       -0.06314
C          6.84908       -1.92855       -1.24431
C          6.17952       -1.83387       -2.46513
H          4.32924       -1.33683       -3.47066
H          4.31768       -0.94337        0.82245
H          6.69196       -1.67462        0.90238
H          7.89515       -2.25547       -1.21185
H          6.69921       -2.08727       -3.39719
C         -0.77009       -2.49449       -1.55743
O         -1.12964       -3.31748       -2.26472
Pd        -0.21530       -1.07776       -0.38186
P         -2.38499       -0.41479        0.46369
P          0.44542        0.77514        0.97390
C          0.47575        2.28135       -0.04209
C         -1.97903        0.00409        2.20152
C         -0.87429        1.04984        2.25941
C         -3.03073        1.11237       -0.28913
C         -3.76319       -1.59717        0.50983
C         -3.81138        2.02107        0.44157
H         -4.08338        1.80822        1.48295
C         -4.32654       -2.01076       -0.70861
H         -3.94482       -1.60798       -1.65637
C          3.06556        1.60216        1.65030
H          2.95612        2.39940        0.90509
C          2.01796        0.70091        1.88230
C          0.38443        3.55432        0.54170
H          0.32053        3.66097        1.63194
C         -4.25161       -2.12975        1.71110
H         -3.82538       -1.82526        2.67336
C         -4.23753        3.20817       -0.15185
H         -4.83832        3.91934        0.42657
C          0.56227        2.16568       -1.43651
H          0.60489        1.16869       -1.89645
C         -5.85759       -3.45659        0.47808
H         -6.67790       -4.18339        0.46654
C          0.38048        4.69209       -0.26350
H          0.30553        5.68330        0.19787
C          2.18440       -0.32656        2.82525
H          1.37426       -1.04751        3.00178
C         -2.69855        1.40054       -1.61990
H         -2.07527        0.69631       -2.18861
C         -3.90075        3.49087       -1.47802
H         -4.23547        4.42698       -1.93975
C         -5.37126       -2.93137       -0.72198
H         -5.80740       -3.24427       -1.67745
C         -3.13817        2.58351       -2.21412
H         -2.87027        2.80341       -3.25403
C          4.25483        1.49132        2.37302
H          5.06678        2.20437        2.19030
C          0.56706        3.30705       -2.23793
H          0.63121        3.20721       -3.32740
C          0.47411        4.56979       -1.65215
H          0.47007        5.46721       -2.28150
C         -5.29578       -3.05627        1.69005
H         -5.67324       -3.46553        2.63411
C          3.37427       -0.43260        3.54219
H          3.49432       -1.23425        4.27972
C          4.40975        0.47907        3.32004
H          5.34495        0.39466        3.88543
H         -0.40322        1.06122        3.25693
H         -1.28712        2.06037        2.09151
H         -2.87064        0.34164        2.76077
H         -1.64312       -0.94078        2.66835
72
Fig.3, L=dppe, Step 6, C35H33OP2Pd, Electronic Energy: -2237.959429 a.u. Gibbs Free Energy: -2237.461635 a.u., Corrected Gibbs Free Energy: -2237.456883 a.u.
Pd         0.01318       -0.00115       -0.89956
C         -0.68692       -1.22097       -2.72764
C          0.70354       -1.30387       -2.47969
H         -1.37260        0.02312       -1.77106
H         -1.00573       -0.59352       -3.57265
H          1.13245       -2.21076       -2.03450
H          1.38582       -0.71994       -3.11166
C         -2.97013       -2.21318       -2.82792
C         -1.65584       -2.27840       -2.34047
C         -1.31194       -3.33028       -1.47732
C         -2.25899       -4.28303       -1.10660
C         -3.56544       -4.20584       -1.59560
C         -3.91652       -3.16889       -2.46222
H         -3.25170       -1.39027       -3.49703
H         -0.29342       -3.40790       -1.08004
H         -1.97238       -5.09671       -0.42980
H         -4.30915       -4.95567       -1.30216
H         -4.93790       -3.10123       -2.85447
C          0.73228        2.23012       -2.29020
O          1.55405        2.90019       -1.87209
P          1.88202       -0.09165        0.53542
P         -0.97429        1.27435        0.76880
C         -2.59651        0.70079        1.35615
C          1.60397        1.23007        1.79383
C          0.14695        1.21627        2.23129
C          1.84542       -1.64462        1.49241
C          3.59324        0.08830       -0.04376
C          2.96016       -2.08822        2.21925
H          3.89615       -1.51520        2.19941
C          4.08713       -0.86614       -0.94905
H          3.44836       -1.69896       -1.27052
C         -1.98910        3.30942       -0.80395
H         -2.52000        2.49696       -1.31871
C         -1.17519        3.02180        0.30497
C         -3.33536        1.45442        2.28070
H         -2.95114        2.41792        2.63991
C          4.42077        1.14693        0.35608
H          4.06221        1.90240        1.06378
C          2.88307       -3.26105        2.96938
H          3.75892       -3.60402        3.53208
C         -3.09950       -0.52534        0.89986
H         -2.52173       -1.11223        0.17053
C          6.20835        0.28957       -1.03231
H          7.23134        0.36850       -1.41768
C         -4.56319        0.98148        2.74081
H         -5.13911        1.57426        3.46067
C         -0.48802        4.06457        0.93930
H          0.15732        3.86898        1.80314
C          0.65707       -2.38849        1.53144
H         -0.21628       -2.04438        0.95770
C          1.69624       -3.99721        3.00372
H          1.64187       -4.92044        3.59207
C          5.38844       -0.76781       -1.43488
H          5.76522       -1.52102       -2.13611
C          0.58207       -3.55911        2.28642
H         -0.35114       -4.13421        2.30803
C         -2.11799        4.61765       -1.26274
H         -2.75807        4.83074       -2.12644
C         -4.32819       -0.99541        1.36488
H         -4.71720       -1.95416        1.00325
C         -5.05960       -0.24214        2.28411
H         -6.02691       -0.60898        2.64633
C          5.72240        1.24408       -0.13945
H          6.36187        2.07421        0.18170
C         -0.61199        5.37364        0.46862
H         -0.06636        6.18152        0.96936
C         -1.42389        5.65251       -0.63012
H         -1.51594        6.68072       -0.99827
H         -0.07970        2.03192        2.94126
H         -0.09624        0.27248        2.75573
H          2.28496        1.09028        2.65368
H          1.86058        2.19686        1.31992
72
Fig.3, L=dppe, Step 7, C35H33OP2Pd, Electronic Energy: -2237.966600 a.u. Gibbs Free Energy: -2237.467623 a.u., Corrected Gibbs Free Energy: -2237.462994 a.u.
Pd        -0.06751        0.06880       -0.91481
C          0.02772       -1.30754       -2.80484
C          1.30901       -1.00679       -2.39009
H         -1.54482        0.14258       -1.57494
H         -0.42450       -0.67665       -3.58131
H          1.90611       -1.71739       -1.80433
H          1.86022       -0.18313       -2.86130
C         -2.03042       -2.68612       -2.96368
C         -0.72905       -2.52300       -2.45783
C         -0.20820       -3.52391       -1.61960
C         -0.97243       -4.63980       -1.28538
C         -2.26873       -4.78365       -1.78690
C         -2.79299       -3.80373       -2.63340
H         -2.44909       -1.90893       -3.61553
H          0.80781       -3.43057       -1.21858
H         -0.54960       -5.40783       -0.62674
H         -2.86834       -5.66190       -1.52097
H         -3.80699       -3.90988       -3.03630
C          0.41437        2.43432       -2.25866
O          1.05748        3.22573       -1.75023
P          1.77534        0.20510        0.61204
P         -1.27865        1.09696        0.71983
C         -2.78930        0.22923        1.23145
C          1.23411        1.45515        1.86018
C         -0.21878        1.19968        2.22588
C          1.89872       -1.34416        1.56556
C          3.47259        0.63406        0.13234
C          3.01151       -1.62963        2.37144
H          3.86017       -0.93490        2.40815
C          4.27975       -0.35334       -0.45878
H          3.90462       -1.37866       -0.56850
C         -2.55679        2.96526       -0.87837
H         -2.94170        2.08916       -1.41693
C         -1.74076        2.79126        0.25207
C         -3.68702        0.83314        2.12430
H         -3.50280        1.85155        2.48997
C          3.97673        1.93610        0.26839
H          3.37225        2.72606        0.72715
C          3.04361       -2.79854        3.13022
H          3.91792       -3.01697        3.75406
C         -3.03552       -1.07051        0.76853
H         -2.33344       -1.53840        0.06389
C          6.06122        1.25376       -0.75526
H          7.07299        1.49609       -1.09996
C         -4.82112        0.13945        2.54374
H         -5.52367        0.61614        3.23671
C         -1.24198        3.91819        0.91862
H         -0.60100        3.81460        1.80096
C          0.82076       -2.24098        1.53861
H         -0.05411       -2.01824        0.91004
C          1.96606       -3.68730        3.09839
H          1.99588       -4.60561        3.69611
C          5.56566       -0.04448       -0.89559
H          6.18630       -0.82575       -1.34892
C          0.85301       -3.40625        2.30524
H          0.00403       -4.09936        2.27769
C         -2.87118        4.24460       -1.32828
H         -3.51119        4.36842       -2.20915
C         -4.16978       -1.76120        1.19486
H         -4.35886       -2.77661        0.82809
C         -5.06273       -1.15611        2.08063
H         -5.95716       -1.69656        2.41127
C          5.26542        2.23991       -0.17277
H          5.64944        3.25957       -0.05494
C         -1.55149        5.19892        0.45609
H         -1.15099        6.07346        0.98116
C         -2.36223        5.36480       -0.66587
H         -2.59860        6.37159       -1.02874
H         -0.61348        1.95937        2.92462
H         -0.33265        0.22361        2.73471
H          1.88897        1.41043        2.75009
H          1.35281        2.45824        1.41012
56
Fig.3, L=dppe, Step 8, C27H25OP2Pd, Electronic Energy: -1928.597862 a.u. Gibbs Free Energy: -1928.223252 a.u., Corrected Gibbs Free Energy: -1928.218386 a.u.
C          1.11455       -0.29246        2.97289
O          1.76673       -0.34761        3.90868
Pd        -0.04108       -0.19679        1.42587
P          1.55689       -0.09280       -0.37675
P         -1.63117       -0.13450       -0.28427
C         -2.88443        1.17162       -0.16838
C          0.60949       -0.53894       -1.89017
C         -0.73278        0.17288       -1.86463
C          2.06808        1.63490       -0.64297
C          3.08591       -1.06675       -0.38070
C          3.07450        1.95309       -1.56746
H          3.59142        1.15559       -2.11678
C          4.00564       -0.84800        0.65826
H          3.79161       -0.09980        1.43298
C         -3.35970       -2.10422        0.61108
H         -3.44536       -1.47468        1.50632
C         -2.52952       -1.70671       -0.44989
C         -3.95196        1.20623       -1.07863
H         -4.05762        0.42163       -1.83902
C          3.37007       -2.02490       -1.36336
H          2.66895       -2.21022       -2.18459
C          3.42071        3.28449       -1.78972
H          4.20905        3.52801       -2.51111
C         -2.76105        2.17533        0.80048
H         -1.92972        2.14021        1.51728
C          5.47320       -2.52575       -0.27484
H          6.40713       -3.09783       -0.23404
C         -4.88427        2.23992       -1.01468
H         -5.71902        2.26310       -1.72440
C         -2.42168       -2.52350       -1.58355
H         -1.78133       -2.23969       -2.42592
C          1.41736        2.66215        0.05438
H          0.63552        2.41245        0.78636
C          2.76591        4.30502       -1.09519
H          3.04223        5.35098       -1.27145
C          5.19442       -1.57114        0.70676
H          5.90766       -1.39115        1.51902
C          1.76468        3.99418       -0.17455
H          1.25290        4.79289        0.37408
C         -4.07958       -3.29310        0.53096
H         -4.72940       -3.59103        1.36151
C         -3.69627        3.20894        0.85756
H         -3.59734        3.99099        1.61871
C         -4.75690        3.24089       -0.04837
H         -5.49385        4.05084       -0.00023
C          4.56158       -2.75038       -1.30602
H          4.77719       -3.49635       -2.07936
C         -3.13962       -3.71891       -1.65374
H         -3.04883       -4.35096       -2.54428
C         -3.96869       -4.10441       -0.60124
H         -4.53151       -5.04290       -0.66078
H         -1.36545       -0.10071       -2.72841
H         -0.59675        1.26992       -1.91580
H          1.18662       -0.27133       -2.79451
H          0.47794       -1.63699       -1.88884
H         -1.33971       -0.21316        2.39359
16
Styrene, C8H8, Electronic Energy: -309.368254 a.u. Gibbs Free Energy: -309.266377 a.u., Corrected Gibbs Free Energy: -309.263489 a.u.
C         -1.94931       -0.53476       -0.00017
C         -2.96964        0.33747        0.00024
H         -4.00924       -0.01335        0.00014
H         -2.82311        1.42651        0.00068
C          0.41052       -1.28502       -0.00000
C         -0.51690       -0.22713       -0.00010
C         -0.01624        1.08952       -0.00014
C          1.35378        1.33262       -0.00004
C          2.26177        0.26842        0.00009
C          1.78351       -1.04245        0.00010
H          0.03889       -2.31766       -0.00000
H         -0.71191        1.93706       -0.00027
H          1.72104        2.36580       -0.00009
H          3.34049        0.46396        0.00016
H          2.48546       -1.88476        0.00018
H         -2.18656       -1.60959       -0.00058
81
Scheme S1, Catalyst, L=PtBu3, Step 1, C24H54P2Pd, Electronic Energy: -1756.696171 a.u. Gibbs Free Energy: -1756.028970 a.u., Corrected Gibbs Free Energy: -1756.025932 a.u.
P          2.33334        0.00001        0.00007
P         -2.33256        0.00042       -0.00078
C         -3.01961       -1.19866       -1.34244
C         -3.01273       -0.56333        1.71106
C         -3.01433        1.76442       -0.36599
C          3.01077        1.60826        0.81708
C          3.01440       -1.50953        0.98478
C          3.01973       -0.09628       -1.79760
C         -2.80141       -2.63979       -0.87319
H         -3.00873       -3.32387       -1.71887
H         -3.47092       -2.94147       -0.05158
H         -1.75498       -2.81826       -0.55979
C         -2.15693       -1.04735       -2.60300
H         -2.47748       -1.79948       -3.35088
H         -1.08785       -1.22994       -2.37819
H         -2.23293       -0.06227       -3.08718
C         -4.49108       -1.01845       -1.71087
H         -4.78995       -1.81510       -2.42096
H         -4.69132       -0.05808       -2.21463
H         -5.16640       -1.09185       -0.84210
C         -2.80181        2.07833       -1.84957
H         -3.00543        3.15369       -2.01765
H         -3.47695        1.52087       -2.51871
H         -1.75771        1.89200       -2.16604
C         -4.48352        1.99894       -0.01942
H         -4.77880        3.01497       -0.34914
H         -5.16143       -0.18582        1.37756
H         -5.16400        1.28869       -0.51814
C         -2.14414        2.77676        0.39162
H         -2.46122        3.80197        0.11557
H         -1.07675        2.66833        0.11632
H         -2.21537        2.70401        1.48717
C         -4.48351       -0.97482        1.74382
H         -4.68026        1.95142        1.06461
H         -4.77808       -1.19436        2.78941
H         -4.68465       -1.89012        1.16253
C         -2.79320        0.56275        2.72521
H         -3.46423        1.42446        2.57862
H         -1.74725        0.92473        2.72111
H         -2.99736        0.17080        3.74050
C         -2.14646       -1.72973        2.20625
H         -2.46443       -2.00452        3.23153
H         -1.07809       -1.44086        2.25058
H         -2.22081       -2.64051        1.59326
C          2.14405        1.92333        2.04428
H          2.23474        1.19067        2.85994
H          1.07236        1.99113        1.77192
H          2.44971        2.90464        2.45823
C          2.79082        2.77765       -0.14658
H          2.98706        3.72463        0.39269
H          1.74729        2.82176       -0.51279
H          3.46763        2.76360       -1.01604
C          4.48105        1.58204        1.23097
H          4.77254        2.58331        1.60624
H          5.16099        1.34086        0.39690
H          4.68256        0.86991        2.04852
C          2.79013       -1.26205        2.47903
H          2.98820       -2.20252        3.02893
H          1.74501       -0.97080        2.69792
H          3.46317       -0.50016        2.90409
C          2.15313       -2.73268        0.64074
H          2.46203       -3.58208        1.28175
H          2.24573       -3.06978       -0.40241
H          1.08056       -2.53564        0.83557
C          4.48629       -1.84899        0.75688
H          4.68993       -2.19918       -0.26884
H          4.78025       -2.67401        1.43599
H          5.16273       -1.00363        0.96621
C          4.49106        0.27489       -1.97387
H          4.78817        0.09954       -3.02709
H          5.16753       -0.32708       -1.34445
H          4.69150        1.33890       -1.76450
C          2.15814        0.80975       -2.68824
H          2.24976        1.88254       -2.46214
H          1.08573        0.54181       -2.61496
H          2.46788        0.67621       -3.74370
C          2.80172       -1.51542       -2.32966
H          3.00358       -1.52223       -3.41836
H          1.75720       -1.85385       -2.19008
H          3.47565       -2.26166       -1.87891
Pd         0.00102       -0.00376       -0.00549
20
Scheme S1, Substrate, Step 1, C9H9ClO, Electronic Energy: -883.307072 a.u. Gibbs Free Energy: -883.188123 a.u., Corrected Gibbs Free Energy: -883.184728 a.u.
C          0.05792        0.86934        0.02098
C          1.15804       -0.17316       -0.00166
H          0.18757        1.51198        0.91279
H          0.18902        1.55354       -0.83855
C          2.51732        0.43297        0.01634
H          1.10015       -0.86337        0.86107
H          1.09744       -0.82828       -0.89091
C         -2.42065        1.22860       -0.03912
C         -1.34609        0.32469        0.00707
C         -1.63890       -1.04473        0.04369
C         -2.96203       -1.49634        0.03642
C         -4.01737       -0.58729       -0.00852
C         -3.73965        0.78215       -0.04677
H         -2.20969        2.30551       -0.06968
H         -0.82964       -1.78300        0.07901
H         -3.16516       -2.57361        0.06593
H         -5.05467       -0.94210       -0.01456
H         -4.56020        1.50887       -0.08357
Cl         3.82100       -0.85319       -0.04181
O          2.82959        1.57466        0.06483
101
Scheme S1, L=PtBu3, Step 2, C33H63ClOP2Pd, Electronic Energy: -2640.013197 a.u. Gibbs Free Energy: -2639.204479 a.u., Corrected Gibbs Free Energy: -2639.199711 a.u.
P          0.71014        2.52408       -0.00259
P          1.89222       -1.96908        0.37584
C          2.09892       -2.35419        2.25395
C          0.73335       -3.30898       -0.37482
C          3.62008       -2.13646       -0.46226
C          1.32909        3.27780       -1.66345
C         -1.15292        2.96717        0.19961
C          1.67955        3.37801        1.43205
C          0.71594       -2.59890        2.86447
H          0.81403       -2.61995        3.96726
H          0.26625       -3.56053        2.56896
H          0.00633       -1.78635        2.61745
C          2.62784       -1.09269        2.94971
H          2.69559       -1.28529        4.03901
H          1.93864       -0.23925        2.80103
H          3.62748       -0.77586        2.61644
C          3.00547       -3.53523        2.59659
H          2.96986       -3.71618        3.68934
H          4.06288       -3.34934        2.34416
H          2.70044       -4.47408        2.10516
C          4.63865       -1.33845        0.35650
H          5.58304       -1.27157       -0.21785
H          4.88914       -1.80469        1.32302
H          4.29530       -0.30202        0.54218
C          4.14211       -3.55977       -0.64909
H          5.16881       -3.51927       -1.06441
H          1.99595       -5.09486       -0.08962
H          4.19909       -4.12899        0.29341
C          3.55842       -1.43766       -1.82769
H          4.57882       -1.39671       -2.25750
H          3.19131       -0.39685       -1.72715
H          2.92174       -1.94792       -2.56555
C          0.96570       -4.74484        0.09062
H          3.53863       -4.14618       -1.36179
H          0.29170       -5.42226       -0.47073
H          0.74001       -4.89232        1.15969
C          0.85432       -3.26270       -1.90027
H          1.79592       -3.69452       -2.27651
H          0.75868       -2.23326       -2.29200
H          0.03181       -3.85735       -2.34337
C         -0.71176       -2.89759       -0.06443
H         -1.40359       -3.58278       -0.59182
H         -0.90668       -1.86599       -0.41821
H         -0.97349       -2.93549        1.00389
C          0.90400        2.33656       -2.79809
H         -0.18308        2.29407       -2.96031
H          1.25746        1.30278       -2.61458
H          1.35853        2.68583       -3.74641
C          2.86002        3.26153       -1.66928
H          3.21476        3.49276       -2.69244
H          3.26467        2.26652       -1.40069
H          3.30883        4.01459       -1.00167
C          0.85055        4.69416       -1.97772
H          1.33145        5.04158       -2.91386
H          1.11041        5.42410       -1.19326
H         -0.23801        4.75091       -2.14446
C         -1.88321        2.65219       -1.10817
H         -2.97531        2.69346       -0.92541
H         -1.65016        1.63631       -1.47666
H         -1.67041        3.37279       -1.91491
C         -1.75094        2.01312        1.24262
H         -2.83636        2.21522        1.33515
H         -1.31921        2.11646        2.24942
H         -1.62649        0.95549        0.93564
C         -1.46050        4.41022        0.59515
H         -1.11076        4.66171        1.61009
H         -2.55839        4.56178        0.59339
H         -1.03305        5.14876       -0.10368
C          1.86477        4.88947        1.30998
H          2.35311        5.27064        2.22893
H          0.91480        5.43813        1.19990
H          2.51840        5.17239        0.46795
C          3.05739        2.71118        1.54800
H          3.71918        2.88822        0.68706
H          2.95902        1.61606        1.67700
H          3.57684        3.11295        2.44073
C          0.97017        3.07093        2.75386
H          1.62324        3.38709        3.59039
H          0.78327        1.98710        2.87838
H          0.01567        3.60734        2.87807
Pd         1.13450        0.22815        0.09353
C         -4.36194       -1.75713       -0.75221
C         -3.41947       -0.86288       -1.53401
H         -5.07298       -2.23433       -1.45403
H         -3.78719       -2.59758       -0.31960
C         -2.67302       -1.60770       -2.58466
H         -3.94751       -0.03426       -2.04414
H         -2.67765       -0.36413       -0.88002
C         -5.91674       -1.85706        1.21117
C         -5.13298       -1.07477        0.34658
C         -5.11374        0.31103        0.54925
C         -5.85274        0.89683        1.58140
C         -6.62688        0.10758        2.42990
C         -6.65594       -1.27691        2.23909
H         -5.94170       -2.94537        1.06957
H         -4.51307        0.95694       -0.10149
H         -5.81755        1.98428        1.72080
H         -7.20561        0.56711        3.23975
H         -7.25905       -1.91061        2.90044
Cl        -1.49551       -0.51385       -3.46980
O         -2.75546       -2.74560       -2.90374
101
Scheme S1, L=PtBu3, Step 3, C33H63ClOP2Pd, Electronic Energy: -2639.989020 a.u. Gibbs Free Energy: -2639.175079 a.u., Corrected Gibbs Free Energy: -2639.172271 a.u.
Pd        -0.49412       -0.23330       -0.35385
P          2.35466       -1.14708        0.21951
C          2.03660       -2.98708        0.68140
C          3.97793       -1.12925       -0.83531
C          2.75028       -0.17691        1.83781
C          1.39044       -3.65780       -0.53893
H          0.57940       -3.03277       -0.95603
H          0.94668       -4.62549       -0.23137
H          2.09645       -3.87562       -1.35415
C          0.96530       -2.99640        1.76884
H          0.10980       -2.36284        1.46608
H          1.32908       -2.65393        2.75197
H          0.58147       -4.02669        1.90527
C          3.22643       -3.82230        1.14898
H          2.86637       -4.82829        1.44479
H          3.73944       -3.39484        2.02620
H          3.97997       -3.98017        0.36016
C          3.94815       -2.23769       -1.89214
H          3.01603       -2.23466       -2.48114
H          4.09829       -3.24521       -1.47259
H          4.78131       -2.06475       -2.60151
C          4.01798        0.18401       -1.62810
H          3.21188        0.20565       -2.38129
H          4.97898        0.24870       -2.17591
H          3.93333        1.09566       -1.01568
C          5.27461       -1.29572       -0.04079
H          6.12305       -1.36408       -0.75105
H          5.28945       -2.21716        0.56484
H          5.49605       -0.44909        0.62799
C          3.59834       -0.88578        2.89138
H          3.78804       -0.19030        3.73348
H          4.58212       -1.21213        2.51633
H          3.09038       -1.76593        3.32050
C          1.40319        0.21208        2.45342
H          0.80392        0.78282        1.71731
H          1.56583        0.86490        3.33537
H          0.79169       -0.64151        2.78784
C          3.40705        1.15849        1.47166
H          2.81020        1.71569        0.72381
H          4.43808        1.06861        1.09535
H          3.45446        1.78898        2.38100
P         -2.76389       -0.18156        0.24634
C         -3.95436        1.20327       -0.40309
C         -3.48107       -1.87121       -0.36468
C         -2.94283       -0.12953        2.18120
C         -3.61044        1.52970       -1.85563
H         -2.60357        1.96411       -1.94078
H         -4.32940        2.28572       -2.22839
H         -3.65261        0.67275       -2.54209
C         -3.68949        2.49746        0.37116
H         -2.60996        2.73173        0.43456
H         -4.10862        2.49757        1.38942
H         -4.17122        3.33615       -0.16796
C         -5.44670        0.87739       -0.32392
H         -6.02026        1.78424       -0.60074
H         -5.78878        0.57701        0.67831
H         -5.74706        0.09019       -1.03511
C         -3.74372       -1.77429       -1.87021
H         -2.86649       -1.38017       -2.41761
H         -4.62129       -1.15905       -2.12632
H         -3.94173       -2.79077       -2.26246
C         -2.38919       -2.93686       -0.21035
H         -1.50248       -2.67792       -0.81766
H         -2.77798       -3.90806       -0.57698
H         -2.05139       -3.09246        0.82624
C         -4.74888       -2.36760        0.32972
H         -5.09554       -3.28963       -0.17771
H         -5.58384       -1.65021        0.29248
H         -4.57909       -2.63800        1.38531
C         -4.35853        0.02003        2.73817
H         -4.30848       -0.04761        3.84322
H         -5.04975       -0.76921        2.40171
H         -4.81535        0.99591        2.50853
C         -2.08441        1.02236        2.72067
H         -1.09130        1.04602        2.24133
H         -1.92779        0.88085        3.80818
H         -2.54366        2.01382        2.59466
C         -2.34322       -1.41333        2.75392
H         -1.31686       -1.58106        2.38625
H         -2.94387       -2.31201        2.53901
H         -2.28553       -1.32421        3.85605
C          0.16348        2.91069       -1.54742
C          0.82950        1.62766       -2.04522
H         -0.03982        3.57781       -2.40652
H         -0.81425        2.65200       -1.10154
C         -0.15566        0.69703       -2.68769
H          1.60529        1.84778       -2.80868
H          1.36147        1.10668       -1.22507
C          0.59641        3.61129        0.83285
C          0.99999        3.60255       -0.50943
C          2.22476        4.20049       -0.84137
C          3.01814        4.79640        0.13954
C          2.59989        4.80482        1.47280
C          1.38540        4.20987        1.81693
H         -0.35664        3.13722        1.10667
H          2.55927        4.20003       -1.88738
H          3.97112        5.26230       -0.13923
H          3.22307        5.27452        2.24316
H          1.04972        4.20635        2.86140
Cl         0.68919       -1.00823       -3.06333
O         -1.09344        0.97151       -3.37531
101
Scheme S1, L=PtBu3, Step 4, C33H63ClOP2Pd, Electronic Energy: -2640.044072 a.u. Gibbs Free Energy: -2639.230947 a.u., Corrected Gibbs Free Energy: -2639.227724 a.u.
Pd        -1.49952       -0.18316       -1.29223
Cl        -0.21936       -0.76357       -3.26908
O         -1.81173        2.48615       -2.05977
C          0.34416        2.03029       -1.10722
H          0.95958        1.83794       -2.00981
H          0.71032        1.31793       -0.34475
C         -1.07327        1.70642       -1.52401
C          1.84976        3.79046       -0.12021
C          0.48027        3.48504       -0.65347
H          0.24246        4.13957       -1.51189
H         -0.27756        3.69791        0.12217
C          2.96049        3.83467       -0.97657
H          2.81853        3.66154       -2.05189
C          2.05567        4.00964        1.24891
H          1.19665        3.97195        1.93243
C          3.33072        4.28160        1.74832
H          3.46962        4.45648        2.82217
C          4.23667        4.10040       -0.48082
H          5.09172        4.13482       -1.16700
C          4.42600        4.32806        0.88472
H          5.42859        4.54039        1.27472
P          2.52277       -1.47593        0.14003
C          2.23099       -3.31078        0.65112
C          3.78764       -1.47981       -1.31336
C          3.36355       -0.58222        1.62532
C          1.21817       -3.89685       -0.34398
H          0.33988       -3.23705       -0.46965
H          0.84977       -4.87035        0.03632
H          1.63754       -4.08614       -1.34339
C          1.53551       -3.33963        2.01568
H          0.63604       -2.69784        2.04226
H          2.19419       -3.04854        2.85002
H          1.19937       -4.37425        2.22373
C          3.45606       -4.22102        0.71617
H          3.14803       -5.22601        1.06943
H          4.22685       -3.85668        1.41575
H          3.93452       -4.36750       -0.26628
C          3.35108       -2.50702       -2.36254
H          2.28853       -2.39372       -2.64458
H          3.52435       -3.54991       -2.05178
H          3.94801       -2.34870       -3.28219
C          3.67357       -0.11575       -2.01010
H          3.96820        0.73913       -1.38229
H          2.64193        0.06232       -2.36635
H          4.33513       -0.10390       -2.89913
C          5.24690       -1.75436       -0.95366
H          5.85228       -1.79275       -1.88189
H          5.38636       -2.72002       -0.43899
H          5.69266       -0.96915       -0.32119
C          4.42875       -1.36607        2.38911
H          4.87386       -0.71730        3.17042
H          5.25548       -1.70685        1.74341
H          4.02117       -2.24897        2.90912
C          2.24372       -0.16686        2.59009
H          1.49055        0.46640        2.08356
H          2.67517        0.43281        3.41668
H          1.71256       -1.01348        3.05105
C          3.97939        0.73380        1.14230
H          3.25267        1.35013        0.57937
H          4.88055        0.60323        0.52156
H          4.28731        1.32286        2.02813
P         -3.06751       -0.04408        0.43247
C         -4.56439        1.08942        0.06238
C         -3.64424       -1.87821        0.44510
C         -2.32497        0.40582        2.13545
C         -4.83587        1.05178       -1.44672
H         -3.94027        1.33734       -2.02624
H         -5.63250        1.78466       -1.67943
H         -5.18645        0.07518       -1.81069
C         -4.21640        2.54124        0.40394
H         -3.29045        2.88425       -0.08787
H         -4.13360        2.72624        1.48684
H         -5.03573        3.18708        0.03484
C         -5.83212        0.70579        0.82611
H         -6.61784        1.45429        0.60577
H         -5.69113        0.69808        1.91965
H         -6.23714       -0.27456        0.52775
C         -4.54406       -2.13983       -0.76603
H         -4.07220       -1.80799       -1.70993
H         -5.54180       -1.68040       -0.68637
H         -4.70230       -3.23194       -0.84941
C         -2.40318       -2.75547        0.22154
H         -1.94980       -2.56832       -0.77462
H         -2.71030       -3.81952        0.22054
H         -1.61455       -2.64361        0.97938
C         -4.37022       -2.32078        1.71306
H         -4.72528       -3.36060        1.57498
H         -5.25559       -1.70401        1.94000
H         -3.71959       -2.32446        2.60282
C         -3.35450        0.60411        3.24689
H         -2.81946        0.75856        4.20386
H         -4.01881       -0.26474        3.38385
H         -3.98557        1.49437        3.09024
C         -1.47941        1.67591        1.98499
H         -0.66564        1.52496        1.25536
H         -1.00428        1.90045        2.95966
H         -2.04813        2.57009        1.69062
C         -1.34198       -0.69350        2.54185
H         -0.59947       -0.88460        1.74311
H         -1.82743       -1.64478        2.81366
H         -0.78273       -0.35293        3.43397
40
Scheme S1, Ligand (L=PtBu3), Step 5, C12H27P, Electronic Energy: -510980.4842009 a.u. Gibbs Free Energy: -813.974314 a.u., Corrected Gibbs Free Energy: -813.971967 a.u.
P          0.00040        0.00057       -0.71452
C          1.77423        0.26120       -0.00706
C         -1.11335        1.40544       -0.00678
C         -0.66078       -1.66649       -0.00717
C          2.18157        1.72253       -0.21762
H          3.26463        1.82514       -0.01004
H          1.66386        2.42285        0.45728
H          2.02042        2.05753       -1.25884
C          2.73606       -0.55871       -0.87968
H          3.77984       -0.32954       -0.58748
H          2.63190       -0.30325       -1.95031
H          2.61169       -1.64746       -0.78232
C          1.99762       -0.09620        1.46110
H          3.03588        0.16441        1.75068
H          1.87768       -1.17370        1.66217
H          1.32606        0.45084        2.14384
C          0.40194       -2.74950       -0.21603
H         -0.05106       -3.73876       -0.00915
H          1.26610       -2.65205        0.46048
H          0.77455       -2.77720       -1.25661
C         -1.08295       -1.68046        1.46083
H         -1.37666       -2.70999        1.74998
H         -1.05134        0.92207        2.14373
H         -0.27421       -1.37269        2.14468
C         -1.85141       -2.09068       -0.87984
H         -2.17284       -3.11015       -0.58861
H         -1.57886       -2.12661       -1.95074
H         -2.73341       -1.44071       -0.78120
C         -0.91502        1.77767        1.46118
H         -1.95609       -1.03756        1.66200
H         -1.66090        2.54528        1.75127
H          0.07781        2.21384        1.66198
C         -2.58229        1.02603       -0.21736
H         -2.93051        0.22742        0.45727
H         -2.79081        0.71801       -1.25849
H         -3.21382        1.91210       -0.01069
C         -0.88591        2.64869       -0.87911
H         -1.60669        3.43721       -0.58574
H         -1.05630        2.43121       -1.94966
H          0.11880        3.08605       -0.78247
137
Scheme S2, Catalyst, L=PPh3,  Step 1, C33H63ClOP2Pd, Electronic Energy: -4270.481202 a.u. Gibbs Free Energy: -4269.503834 a.u., Corrected Gibbs Free Energy: -4269.496041 a.u.
Pd         1.39963       -0.02776       -0.28878
P          3.55369       -0.48960        0.54839
P         -4.35085       -0.05435        0.18649
C         -5.92280        0.15304       -0.74931
C          3.65114       -1.36448        2.16468
C         -4.82214       -1.37046        1.38312
C          4.48484       -1.56971       -0.61573
C          4.71048        0.91385        0.80859
C         -5.14593       -1.15310        2.72986
H         -5.14612       -0.13598        3.14059
C          5.49806       -2.45499       -0.22331
H          5.79736       -2.52186        0.83015
C          5.66399        1.29032       -0.14920
H          5.80898        0.68148       -1.05109
C         -5.12772        2.57590        0.98760
H         -5.91875        2.52924        0.22889
C         -4.30718        1.46260        1.21995
C         -7.18588       -0.10025       -0.19173
H         -7.26745       -0.45076        0.84544
C          4.54785        1.72524        1.94637
H          3.80754        1.45332        2.71042
C         -5.19073       -3.75371        1.71857
H         -5.20420       -4.77324        1.31469
C          2.50625       -2.04073        2.61159
H          1.59546       -2.01056        1.99630
C         -4.84157       -2.68714        0.89181
H         -4.58547       -2.87911       -0.15960
C         -5.50747       -3.52557        3.05982
H         -5.77301       -4.36415        3.71435
C          4.80036       -1.38202        2.97181
H          5.70517       -0.84956        2.65216
C          6.13195       -3.26804       -1.16508
H          6.91671       -3.96247       -0.84186
C          3.66108       -2.75183        4.61108
H          3.66702       -3.29077        5.56581
C         -5.85023        0.60222       -2.07646
H         -4.86997        0.79500       -2.53076
C         -5.48106       -2.22378        3.56171
H         -5.73240       -2.03478        4.61238
C          6.27828        3.22788        1.17068
H          6.89006        4.12684        1.31126
C          2.51006       -2.73515        3.82230
H          1.60503       -3.25803        4.15429
C         -8.34496        0.09623       -0.94219
H         -9.32464       -0.10548       -0.49276
C         -3.30070        1.56748        2.19764
H         -2.64019        0.71191        2.39332
C          4.12394       -1.51434       -1.97177
H          3.30914       -0.84175       -2.28147
C          5.77011       -3.19908       -2.51173
H          6.26731       -3.84113       -3.24864
C          4.80433       -2.07132        4.18444
H          5.70987       -2.07745        4.80272
C          6.44069        2.43689        0.03302
H          7.18223        2.71270       -0.72692
C          4.76672       -2.31520       -2.91507
H          4.47097       -2.26064       -3.96971
C         -4.93973        3.76222        1.70146
H         -5.58638        4.62395        1.49715
C         -7.01026        0.80526       -2.82619
H         -6.93494        1.15786       -3.86175
C         -8.26014        0.55087       -2.26046
H         -9.17256        0.70371       -2.84884
C          5.32579        2.86659        2.12785
H          5.18750        3.47962        3.02691
C         -3.12673        2.74348        2.92298
H         -2.34241        2.79850        3.68730
C         -3.93933        3.85194        2.66864
H         -3.79091        4.78405        3.22698
P          0.08642       -1.86894       -0.87665
C          0.97216       -3.32980       -1.55647
C         -0.71658       -2.53195        0.63954
C         -1.31810       -1.68480       -2.05374
C         -0.93324       -3.89527        0.88895
H         -0.66434       -4.64304        0.13240
C         -2.38205       -2.59704       -2.11201
H         -2.39576       -3.46922       -1.44463
C         -1.32076       -0.58388       -2.92035
H         -0.49223        0.13888       -2.87314
C          1.94568       -3.94826       -0.75130
H          2.09980       -3.59870        0.28010
C          0.82093       -3.77097       -2.87869
H          0.07602       -3.30320       -3.53449
C         -1.48064       -4.31548        2.10285
H         -1.63971       -5.38527        2.28482
C          2.56397       -5.42411       -2.56458
H          3.18407       -6.23858       -2.95752
C         -3.42011       -1.30670       -3.87578
H         -4.24660       -1.15543       -4.58070
C          2.72359       -4.99241       -1.24348
H          3.46978       -5.46715       -0.59463
C         -1.06986       -1.60091        1.63084
H         -0.87606       -0.53170        1.45114
C         -1.82618       -3.38084        3.08100
H         -2.25117       -3.71430        4.03539
C          1.61546       -4.80695       -3.37906
H          1.48460       -5.13539       -4.41717
C         -3.43131       -2.40387       -3.01047
H         -4.26488       -3.11657       -3.03733
C         -1.62412       -2.01993        2.84021
H         -1.88793       -1.27974        3.60573
C         -2.36091       -0.39885       -3.83345
H         -2.34710        0.46451       -4.50991
P          0.93492        2.25706       -0.51242
C          0.64763        3.10891        1.09046
C          2.37531        3.13018       -1.24852
C         -0.47158        2.89617       -1.51590
C          2.96378        4.28376       -0.71301
H          2.55971        4.73906        0.19970
C         -0.32699        3.58198       -2.72998
H          0.67121        3.84167       -3.10352
C         -1.76879        2.58657       -1.07129
H         -1.90443        2.03030       -0.13184
C          0.96956        2.42717        2.27324
H          1.35149        1.39644        2.20884
C          0.13263        4.41204        1.17921
H         -0.13245        4.95973        0.26520
C          4.07365        4.86598       -1.33106
H          4.52591        5.76468       -0.89410
C          0.30907        4.34238        3.59167
H          0.17768        4.82588        4.56704
C         -2.73233        3.65052       -3.01918
H         -3.61228        3.94322       -3.60421
C          0.80831        3.04125        3.51658
H          1.06776        2.49634        4.43207
C          2.93686        2.56462       -2.40740
H          2.49712        1.64777       -2.82699
C          4.60562        4.31130       -2.49508
H          5.47464        4.77274       -2.97897
C         -0.03445        5.02417        2.42125
H         -0.43367        6.04408        2.47661
C         -1.44959        3.94907       -3.47806
H         -1.31507        4.48389       -4.42608
C          4.03347        3.15510       -3.03253
H          4.44962        2.70484       -3.94174
C         -2.88677        2.97124       -1.80656
H         -3.89041        2.72873       -1.43423
34
Scheme S2, Ligand (L=PPh3), Step 2, C18H15P, Electronic Energy: -1035.584021 a.u. Gibbs Free Energy: -1035.358032 a.u., Corrected Gibbs Free Energy: -1035.353751 a.u.
P          0.00448        0.00251       -1.23644
C          1.65200        0.09931       -0.42911
C         -0.90819        1.38021       -0.43326
C         -0.73778       -1.47241       -0.42962
C         -0.40905        2.14785        0.62877
H          0.58569        1.93835        1.04160
C         -1.60607       -1.41649        0.67013
H         -1.87869       -0.44877        1.10946
C         -0.40964       -2.72904       -0.96520
H          0.26128       -2.79206       -1.83265
C          2.56107        1.04142       -0.93941
H          2.26590        1.67983       -1.78322
C          2.05518       -0.71312        0.64030
H          1.36583       -1.45738        1.05819
C         -1.17255        3.18072        1.17710
H         -0.76749        3.77157        2.00735
C          4.22264        0.36643        0.68176
H          5.22453        0.46870        1.11485
C         -1.78478       -3.83137        0.68944
H         -2.19498       -4.74981        1.12540
C          3.83133        1.18176       -0.38294
H          4.52473        1.92726       -0.78998
C         -2.18652        1.67662       -0.93592
H         -2.59061        1.09245       -1.77400
C         -2.44659        3.45628        0.67931
H         -3.04448        4.26615        1.11351
C          3.33312       -0.58210        1.18794
H          3.63303       -1.22596        2.02339
C         -2.12787       -2.58807        1.22206
H         -2.80584       -2.52688        2.08178
C         -2.95376        2.69800       -0.37860
H         -3.95222        2.90967       -0.77927
C         -0.92018       -3.89923       -0.40547
H         -0.64808       -4.87132       -0.83347
103
Scheme S2, L=PPh3,  Step 2, C54H45P3Pd, Electronic Energy: -3234.879111 a.u. Gibbs Free Energy: -3234.157934 a.u., Corrected Gibbs Free Energy: -3234.149388 a.u.
Pd        -0.07196        0.04768        0.00306
P          0.56998       -2.20794        0.01588
C          0.79779       -2.83481       -1.69375
C          2.14616       -2.65305        0.84567
C          2.20036       -3.31768        2.07895
H          1.28264       -3.70762        2.53687
C         -1.02647       -4.58041        0.15362
H         -0.53110       -4.92063       -0.76450
C         -0.64564       -3.37279        0.75448
C          1.70390       -3.84831       -2.03938
H          2.31933       -4.32339       -1.26502
C          4.56069       -2.35316        0.94543
H          5.48454       -1.97507        0.49047
C          3.34529       -2.16855        0.29113
H          3.32565       -1.64119       -0.67276
C          4.60212       -3.01087        2.17902
H          5.55711       -3.14947        2.69918
C          0.01775       -2.25149       -2.70574
H         -0.67854       -1.44003       -2.44522
C          3.41919       -3.49094        2.74067
H          3.44076       -4.01318        3.70479
C          1.82985       -4.26299       -3.36601
H          2.54521       -5.05348       -3.62224
C         -1.30292       -2.96479        1.92799
H         -1.02656       -2.00852        2.39712
C         -2.05151       -5.35324        0.70504
H         -2.34862       -6.28851        0.21553
C          0.13238       -2.67684       -4.02913
H         -0.48516       -2.21209       -4.80673
C          1.04355       -3.68115       -4.36267
H          1.14397       -4.00974       -5.40381
C         -2.31123       -3.74581        2.48914
H         -2.81087       -3.41456        3.40755
C         -2.69659       -4.93900        1.87064
H         -3.50377       -5.54490        2.29869
P          1.68425        1.60091       -0.01799
C          1.38148        3.36974       -0.41968
C          2.63531        1.72720        1.54956
C          2.93532        1.09166       -1.26487
C          3.47747        2.80884        1.85197
H          3.58639        3.63595        1.13836
C          4.32062        1.15660       -1.06494
H          4.72723        1.59548       -0.14505
C          2.45028        0.51512       -2.45157
H          1.36312        0.44473       -2.60813
C          0.57983        4.11226        0.46668
H          0.20140        3.64003        1.38483
C          1.82732        3.98666       -1.59682
H          2.45137        3.43122       -2.30821
C          4.18589        2.84026        3.05298
H          4.84170        3.69019        3.27621
C          0.71059        6.04644       -0.97955
H          0.45000        7.08887       -1.19781
C          4.70583        0.06953       -3.19561
H          5.39769       -0.33816       -3.94202
C          0.25827        5.43949        0.19679
H         -0.36111        6.00387        0.90463
C          2.50952        0.68659        2.48271
H          1.83109       -0.15149        2.26215
C          4.06318        1.79192        3.96838
H          4.62051        1.81925        4.91214
C          1.48999        5.31449       -1.87484
H          1.84899        5.78133       -2.80004
C          5.19881        0.64349       -2.02308
H          6.28024        0.68930       -1.84670
C          3.22347        0.71455        3.68179
H          3.11522       -0.10707        4.40003
C          3.32591        0.01381       -3.41282
H          2.92892       -0.43665       -4.33077
P         -2.31800        0.68104       -0.02058
C         -2.98132        0.53802        1.68581
C         -2.67603        2.42239       -0.48557
C         -3.55572       -0.24885       -1.01558
C         -3.40599        3.31501        0.31090
H         -3.83583        2.97929        1.26321
C         -4.63863        0.34904       -1.67575
H         -4.78811        1.43474       -1.62095
C         -3.39705       -1.64117       -1.10358
H         -2.54064       -2.11501       -0.60309
C         -2.14356        0.93743        2.74257
H         -1.14637        1.34424        2.51629
C         -4.23812       -0.00312        1.99072
H         -4.91087       -0.32462        1.18590
C         -3.59844        4.63690       -0.10023
H         -4.16819        5.32486        0.53611
C         -3.80898        0.26067        4.35974
H         -4.13056        0.14747        5.40171
C         -5.37931       -1.81456       -2.47448
H         -6.08970       -2.42284       -3.04663
C         -2.55628        0.80747        4.06710
H         -1.89102        1.12522        4.87863
C         -2.13881        2.88480       -1.69974
H         -1.54066        2.20303       -2.32255
C         -3.07724        5.07950       -1.31617
H         -3.23061        6.11679       -1.63702
C         -4.64609       -0.14356        3.31943
H         -5.63016       -0.57342        3.54149
C         -5.54076       -0.42996       -2.40378
H         -6.38149        0.05151       -2.91744
C         -2.34873        4.19621       -2.11894
H         -1.92674        4.53831       -3.07177
C         -4.30493       -2.42065       -1.81817
H         -4.16685       -3.50753       -1.87274
123
Scheme S2, L=PPh3,  Step 3, C63H54ClOP3Pd, Electronic Energy: -4118.203233 a.u. Gibbs Free Energy: -4117.334818 a.u., Corrected Gibbs Free Energy: -4117.327437 a.u.
Pd        -0.65155        0.07212       -0.06181
P         -2.34736       -1.50744        0.39225
C         -2.79583       -1.83237        2.14751
C         -3.93532       -0.94771       -0.36075
C         -2.17587       -3.20355       -0.29937
C         -5.19618       -1.31966        0.12537
H         -5.28005       -1.99170        0.98871
C         -2.72732       -3.55625       -1.54117
H         -3.37964       -2.85264       -2.07421
C         -1.34205       -4.13328        0.34827
H         -0.89402       -3.88251        1.31961
C         -2.45936       -0.85762        3.09909
H         -1.91295        0.04065        2.77612
C         -3.45592       -2.99348        2.58073
H         -3.72513       -3.77462        1.85864
C         -6.35926       -0.83403       -0.47562
H         -7.33845       -1.12596       -0.07744
C         -3.44723       -2.18282        4.86150
H         -3.69928       -2.32252        5.91934
C         -1.62709       -5.71333       -1.46309
H         -1.41365       -6.68877       -1.91572
C         -2.78728       -1.02616        4.44468
H         -2.51308       -0.25376        5.17289
C         -3.86704       -0.08534       -1.46597
H         -2.87982        0.23249       -1.83295
C         -6.27849        0.01870       -1.57827
H         -7.19335        0.40107       -2.04655
C         -3.77771       -3.16707        3.92703
H         -4.29361       -4.07949        4.24899
C         -2.45451       -4.79940       -2.11631
H         -2.89676       -5.05378       -3.08751
C         -5.02745        0.38772       -2.07753
H         -4.95410        1.06313       -2.93867
C         -1.07357       -5.37479       -0.22498
H         -0.42355       -6.08506        0.30079
P         -1.12964        2.33463        0.31563
C         -2.89997        2.84845        0.27662
C         -0.55256        2.97340        1.93719
C         -0.37540        3.50882       -0.88204
C         -1.28137        3.87240        2.72920
H         -2.25295        4.24843        2.38517
C          0.31051        4.67368       -0.51344
H          0.40346        4.94905        0.54471
C         -0.47436        3.18838       -2.24658
H         -0.99494        2.26719       -2.54723
C         -3.80201        2.13971        1.08838
H         -3.43081        1.32775        1.72920
C         -3.40371        3.85798       -0.55550
H         -2.72810        4.43416       -1.19908
C         -0.77780        4.30207        3.95851
H         -1.36027        5.00317        4.56813
C         -5.65372        3.44266        0.24190
H         -6.72607        3.67073        0.22359
C          0.76291        5.17770       -2.83976
H          1.21134        5.82651       -3.60160
C         -5.16149        2.44032        1.08330
H         -5.84537        1.87732        1.73025
C          0.69159        2.51747        2.40394
H          1.26227        1.79901        1.79763
C          0.46264        3.84765        4.40912
H          0.85532        4.18633        5.37502
C         -4.77151        4.14624       -0.57730
H         -5.14694        4.93530       -1.23995
C          0.88087        5.49839       -1.48724
H          1.41904        6.40413       -1.18253
C          1.19942        2.95579        3.62577
H          2.17318        2.59105        3.97458
C          0.07851        4.01872       -3.21836
H         -0.01248        3.75345       -4.27877
P          1.08817       -0.57619       -1.50469
C          2.40413       -1.69536       -0.87974
C          0.38628       -1.51400       -2.92081
C          2.08172        0.73782       -2.32219
C          0.81793       -2.78981       -3.30930
H          1.65981       -3.26961       -2.79498
C          2.35870        0.78102       -3.69484
H          1.97662       -0.00351       -4.36020
C          2.59069        1.75478       -1.49796
H          2.35408        1.74640       -0.42323
C          2.00957       -2.72718       -0.01324
H          0.94611       -2.83358        0.23852
C          3.76643       -1.55183       -1.18034
H          4.10638       -0.75592       -1.85492
C          0.18327       -3.46468       -4.35577
H          0.53080       -4.46462       -4.64297
C          4.30542       -3.43712        0.24251
H          5.04959       -4.10890        0.68718
C          3.64682        2.81112       -3.39750
H          4.25379        3.62127       -3.81893
C          2.94802       -3.59677        0.53821
H          2.61942       -4.39600        1.21457
C         -0.69515       -0.93261       -3.60612
H         -1.04894        0.06450       -3.30902
C         -0.88354       -2.87446       -5.03341
H         -1.37921       -3.40743       -5.85339
C          4.70946       -2.41557       -0.61833
H          5.77218       -2.28456       -0.85736
C          3.12962        1.81717       -4.22897
H          3.33411        1.84123       -5.30614
C         -1.31960       -1.60079       -4.65684
H         -2.15847       -1.12714       -5.18109
C          3.37905        2.77459       -2.02579
H          3.77443        3.55634       -1.36545
C          5.01566       -0.94730        2.73168
C          3.54738       -0.64344        2.49294
H          5.27451       -0.68327        3.77646
H          5.17690       -2.03904        2.67005
C          2.64429       -1.56976        3.22947
H          3.27532        0.38883        2.78335
H          3.27960       -0.71156        1.41896
C          7.26732       -0.76833        1.64111
C          5.96403       -0.26566        1.78231
C          5.59785        0.84460        1.00916
C          6.50197        1.42713        0.11688
C          7.79133        0.91277       -0.01636
C          8.17292       -0.18791        0.75525
H          7.56859       -1.64279        2.23276
H          4.58863        1.26645        1.09335
H          6.19212        2.29240       -0.48144
H          8.49869        1.36741       -0.71981
H          9.18337       -0.60323        0.65925
Cl         0.88205       -1.17690        2.92100
O          2.91894       -2.47453        3.94510
89
Scheme S2, L=PPh3,  Step 4, C45H39ClOP2Pd, Electronic Energy: -3082.584175 a.u. Gibbs Free Energy: -3081.968359 a.u., Corrected Gibbs Free Energy: -3081.962287 a.u.
Pd         0.10967       -0.58820       -0.14056
P          2.40436       -0.49021       -0.35223
C          3.34884       -1.24448        1.03329
C          3.09051       -1.35755       -1.82185
C          4.32897       -1.04388       -2.40252
H          4.92974       -0.21395       -2.00991
C          3.54967        1.88356        0.66673
H          3.57410        1.37450        1.63908
C          3.10335        1.19932       -0.47393
C          4.75117       -1.21415        1.08373
H          5.32027       -0.71186        0.29054
C          2.82015       -3.15489       -3.43758
H          2.22286       -3.98016       -3.84243
C          2.34055       -2.41649       -2.35532
H          1.36363       -2.65733       -1.91002
C          4.05277       -2.83462       -4.00820
H          4.42888       -3.40767       -4.86383
C          2.64428       -1.88451        2.06114
H          1.54470       -1.90189        2.02368
C          4.80383       -1.77696       -3.49036
H          5.77087       -1.51891       -3.93798
C          5.43142       -1.81136        2.14333
H          6.52690       -1.77996        2.17430
C          3.06277        1.88687       -1.69928
H          2.69941        1.37797       -2.60182
C          3.96725        3.21281        0.57959
H          4.31233        3.73062        1.48215
C          3.32591       -2.48375        3.12264
H          2.76301       -2.97951        3.92210
C          4.71953       -2.44784        3.16433
H          5.25694       -2.91683        3.99696
C          3.48308        3.21297       -1.78454
H          3.45239        3.73052       -2.75070
C          3.94033        3.88022       -0.64511
H          4.27120        4.92312       -0.71265
P         -2.16019       -0.92131        0.12938
C         -3.13946       -0.99675       -1.42470
C         -2.62607       -2.48388        0.98127
C         -2.99922        0.36546        1.12450
C         -3.92156       -2.71901        1.46753
H         -4.69421       -1.94493        1.37463
C         -2.96617        0.29262        2.52683
H         -2.53889       -0.59025        3.02025
C         -3.52332        1.51914        0.52219
H         -3.53805        1.61230       -0.57191
C         -2.45519       -1.26657       -2.61826
H         -1.36230       -1.39298       -2.59090
C         -4.53110       -0.81861       -1.46584
H         -5.08759       -0.60226       -0.54515
C         -4.23459       -3.93066        2.08183
H         -5.24869       -4.10218        2.46163
C         -4.52522       -1.16785       -3.86070
H         -5.06757       -1.22850       -4.81157
C         -3.99437        2.47685        2.69551
H         -4.38628        3.29761        3.30744
C         -3.14330       -1.35674       -3.82934
H         -2.59400       -1.56588       -4.75482
C         -1.65446       -3.48378        1.12294
H         -0.63678       -3.29614        0.74869
C         -3.25964       -4.92325        2.21488
H         -3.50828       -5.87460        2.69982
C         -5.21730       -0.89820       -2.67703
H         -6.30321       -0.74861       -2.69729
C         -3.46025        1.33874        3.30487
H         -3.42623        1.26385        4.39833
C         -1.96956       -4.69908        1.73405
H         -1.19982       -5.47249        1.83944
C         -4.02337        2.56265        1.30271
H         -4.43668        3.45312        0.81353
C          0.01469        3.66488        0.33778
C         -0.09866        2.53152        1.34867
H         -0.23804        4.62491        0.82228
H          1.07081        3.74216        0.01267
C          0.79822        2.68441        2.51636
H         -1.13136        2.42890        1.73889
H          0.10972        1.53421        0.87630
C         -2.00611        4.22236       -1.08869
C         -0.87665        3.42915       -0.85097
C         -0.60969        2.37121       -1.73422
C         -1.44942        2.11025       -2.81725
C         -2.57885        2.90306       -3.03652
C         -2.85127        3.96395       -2.17055
H         -2.23104        5.05382       -0.40793
H          0.27536        1.73873       -1.56714
H         -1.21464        1.28372       -3.49892
H         -3.24036        2.69935       -3.88757
H         -3.73200        4.59641       -2.33616
Cl         0.72977        1.18788        3.59918
O          1.50432        3.58429        2.82688
89
Scheme S2, L=PPh3,  Step 5, C45H39ClOP2Pd, Electronic Energy: -3082.581076 a.u. Gibbs Free Energy: -3081.964630 a.u., Corrected Gibbs Free Energy: -3081.958617 a.u.
Pd        -0.22645       -0.24027       -0.35754
P         -2.47577       -0.06503        0.14216
P          2.01759       -0.86311        0.10776
Cl         0.54043       -0.91881       -3.34972
O         -1.53891        0.75042       -2.91187
C          2.42056       -2.54275       -0.51335
C         -3.17338        1.62234        0.08281
C          3.47653        0.13324       -0.37950
C         -3.61185       -1.07523       -0.88557
C         -2.85862       -0.64165        1.84556
C          4.16540        0.94786        0.53103
H          3.89139        0.94374        1.59335
C         -5.00443       -1.04249       -0.71684
H         -5.45382       -0.36966        0.02552
C         -3.96252       -0.18963        2.58473
H         -4.63666        0.56682        2.16327
C          3.25180       -1.76280        2.51264
H          3.98469       -2.27877        1.87864
C          0.62384        1.73476       -2.40300
H          0.94404        2.08731       -3.40588
H          1.52697        1.31684       -1.93233
C          2.21207       -1.02256        1.92947
C          3.72804       -2.99047       -0.75286
H          4.58028       -2.32005       -0.58538
C         -2.01140       -1.60503        2.41317
H         -1.13625       -1.95355        1.84338
C          4.89045        0.99186       -2.16310
H          5.17079        1.00386       -3.22301
C         -3.87856        2.09220       -1.03441
H         -4.14517        1.40403       -1.84512
C          3.84888        0.17135       -1.73524
H          3.31430       -0.44937       -2.46641
C         -0.37678        0.64228       -2.64702
C          5.57391        1.79581       -1.24697
H          6.39275        2.44210       -1.58404
C         -2.83000        2.53169        1.09810
H         -2.26762        2.18561        1.97607
C         -5.82702       -1.85808       -1.49243
H         -6.91413       -1.82460       -1.35427
C         -3.88754        4.33411       -0.11888
H         -4.16476        5.39165       -0.19922
C          1.35000       -3.42079       -0.74383
H          0.32099       -3.06573       -0.57965
C          5.20741        1.77098        0.09852
H          5.73600        2.39988        0.82513
C         -3.36080       -1.65315        4.41712
H         -3.55588       -2.04301        5.42303
C         -4.23315        3.43904       -1.13202
H         -4.78445        3.79098       -2.01206
C          3.95753       -4.29031       -1.20649
H          4.98445       -4.62712       -1.39113
C          1.29285       -0.37057        2.76337
H          0.46892        0.20158        2.30905
C         -3.05951       -1.93789       -1.84145
H         -1.96874       -1.95559       -1.98074
C         -5.26726       -2.71757       -2.44192
H         -5.91594       -3.35920       -3.04989
C         -3.18717        3.87478        0.99991
H         -2.91265        4.56998        1.80217
C         -4.20878       -0.69133        3.86296
H         -5.07204       -0.32671        4.43213
C         -3.88349       -2.75693       -2.61575
H         -3.44060       -3.42735       -3.36155
C          3.36638       -1.84757        3.89952
H          4.18125       -2.43141        4.34344
C          1.58052       -4.72195       -1.18866
H          0.73416       -5.39620       -1.36418
C          2.88604       -5.15857       -1.42287
H          3.06902       -6.17847       -1.78109
C          1.01702        3.42341       -0.56990
C         -2.26212       -2.11175        3.68871
H         -1.58781       -2.86172        4.11918
C          0.03038        2.87833       -1.56388
H         -0.33257        3.68022       -2.23328
H         -0.85429        2.50170       -1.01848
C          1.41023       -0.45120        4.15230
H          0.68153        0.06183        4.79136
C          2.44625       -1.19166        4.72193
H          2.53752       -1.26197        5.81220
C          2.07491        4.25215       -0.97128
H          2.16669        4.53416       -2.02878
C          0.92468        3.07043        0.78434
H          0.10115        2.41663        1.10649
C          1.85095        3.54364        1.71623
H          1.75680        3.26051        2.77207
C          3.00193        4.72828       -0.04328
H          3.81978        5.37964       -0.37538
C          2.89140        4.37811        1.30482
H          3.61961        4.75402        2.03363
58
Scheme S3, L=PtBu3, Step 7 (minus CO), C20H36PPd, Electronic Energy: -1252.170507 a.u. Gibbs Free Energy:  -1251.716951 a.u., Corrected Gibbs Free Energy: -1251.713904 a.u.
P          1.44290        0.23042       -0.04049
C          0.76306        2.01569        0.07252
C          2.70050       -0.08129        1.36895
C          2.27833       -0.04417       -1.73788
C          0.38368        2.30924        1.52658
H         -0.17102        3.26621        1.55714
H          1.25376        2.42640        2.19205
H         -0.28437        1.53475        1.94811
C         -0.54691        2.10177       -0.72158
H         -0.98377        3.10813       -0.57234
H         -1.28645        1.36470       -0.35913
H         -0.42970        1.96281       -1.80620
C          1.73321        3.08962       -0.41781
H          1.28975        4.08683       -0.23092
H          1.92705        3.02703       -1.50150
H          2.70455        3.06386        0.10378
C          1.37519        0.52107       -2.83707
H          1.77987        0.20568       -3.81728
H          1.33769        1.62196       -2.84934
H          0.34206        0.13189       -2.77297
C          3.66803        0.57637       -1.87130
H          4.03250        0.42399       -2.90574
H          4.29183        1.29047        0.70461
H          3.67347        1.66289       -1.68247
C          2.35820       -1.55509       -1.99378
H          2.70141       -1.72195       -3.03284
H          1.36703       -2.03798       -1.88965
H          3.06390       -2.08430       -1.33721
C          3.70628        1.04246        1.60593
H          4.40992        0.11100       -1.20178
H          4.42644        0.72279        2.38425
H          3.23403        1.96912        1.97191
C          3.46015       -1.37723        1.07250
H          4.17892       -1.28451        0.24278
H          2.77859       -2.22162        0.85799
H          4.04523       -1.65275        1.97037
C          1.90931       -0.34762        2.65792
H          2.61799       -0.64386        3.45497
H          1.19291       -1.18564        2.54137
H          1.35224        0.52239        3.03364
Pd        -0.28831       -1.36835        0.27425
C         -2.37395       -1.62041       -0.63215
C         -1.98785       -2.62452        0.30356
H         -1.20016       -0.93798       -1.00328
H         -2.46181       -1.95173       -1.68142
H         -2.40271       -2.61488        1.32177
H         -1.66517       -3.60485       -0.07598
C         -4.14394        0.02980       -1.25176
C         -3.30025       -0.50924       -0.27288
C         -3.32037        0.03919        1.01836
C         -4.17616        1.09248        1.32675
C         -5.02015        1.62077        0.34475
C         -5.00225        1.08657       -0.94357
H         -4.12545       -0.38413       -2.26749
H         -2.63309       -0.35100        1.78188
H         -4.17790        1.51461        2.33833
H         -5.68712        2.45664        0.58537
H         -5.65809        1.49828       -1.71934
94
Scheme S4, L=PPh3, Step 3, C47H45NOP2Pd, Electronic Energy: -2755.028656 a.u. Gibbs Free Energy: -2754.366885 a.u., Corrected Gibbs Free Energy: -2754.360763 a.u.
Pd        -0.13733       -0.58354       -0.75340
P          2.23219       -0.80842        0.17501
P         -0.51908        1.61211       -0.12338
O         -2.07865       -0.38314       -2.80381
C         -0.12740        1.78991        1.65241
C          3.34920        0.61798        0.41458
C          0.50640        2.78530       -1.07242
C          2.24421       -1.69896        1.76942
C          3.15121       -1.89048       -0.98144
C          0.31983        4.17509       -0.97769
H         -0.46579        4.58621       -0.33206
C          3.30760       -1.63093        2.68188
H          4.18825       -1.01620        2.45854
C          4.09503       -2.83324       -0.55358
H          4.31331       -2.95172        0.51518
C         -3.08004        2.36200        0.81377
H         -2.74277        2.05012        1.80999
C         -3.09535       -1.04168       -0.72555
H         -3.04564       -0.46111        0.21597
H         -2.85572       -2.08360       -0.42813
C         -2.20803        2.29621       -0.28218
C          0.29840        2.99367        2.23038
H          0.42785        3.89365        1.61854
C          2.88350       -1.76324       -2.35325
H          2.12263       -1.04544       -2.69346
C          2.27386        3.15580       -2.69517
H          3.03228        2.75079       -3.37540
C          3.20175        1.43124        1.55020
H          2.50336        1.14407        2.34629
C          1.47943        2.28521       -1.94842
H          1.60864        1.19813       -2.04942
C         -1.97123       -0.59989       -1.62610
C          2.10191        4.53418       -2.57381
H          2.72664        5.21933       -3.15846
C          4.27273        0.99452       -0.57212
H          4.40576        0.37760       -1.46963
C          3.25425       -2.34599        3.87848
H          4.08947       -2.28279        4.58558
C          4.85741        2.97329        0.69234
H          5.44300        3.89372        0.79902
C         -0.27191        0.65364        2.46221
H         -0.60905       -0.29149        2.01311
C          1.12113        5.04192       -1.71783
H          0.97153        6.12427       -1.63247
C          4.49946       -3.49038       -2.84776
H          5.02547       -4.11852       -3.57612
C          3.94988        2.59983        1.68582
H          3.82324        3.22229        2.57975
C          0.58906        3.05111        3.59294
H          0.93305        3.99414        4.03326
C         -2.66738        2.69420       -1.54817
H         -1.99989        2.64310       -2.41789
C          1.13207       -2.49845        2.07673
H          0.28428       -2.54049        1.37857
C          2.14603       -3.14278        4.17286
H          2.10772       -3.70276        5.11443
C          5.02206        2.16272       -0.43134
H          5.73832        2.44261       -1.21282
C          4.76256       -3.63126       -1.48417
H          5.49591       -4.36908       -1.13855
C          1.08589       -3.22166        3.26796
H          0.21080       -3.84086        3.49618
C         -4.38456        2.82869        0.64668
H         -5.05595        2.87877        1.51171
C          0.01667        0.71430        3.82566
H         -0.09613       -0.18159        4.44755
C          0.45424        1.91297        4.39106
H          0.69089        1.96178        5.46022
C         -5.55744       -1.44666       -0.44725
C          3.56013       -2.55254       -3.28236
H          3.34490       -2.44201       -4.35145
C         -4.47801       -0.95715       -1.36926
H         -4.67211        0.09051       -1.66391
H         -4.46974       -1.55242       -2.30038
C         -3.97024        3.16173       -1.70941
H         -4.31421        3.47658       -2.70138
C         -4.83204        3.23047       -0.61233
H         -5.85670        3.59827       -0.74026
C         -6.34254       -0.55031        0.29130
H         -6.18833        0.52918        0.16248
C         -5.77720       -2.82169       -0.27250
H         -5.17341       -3.53821       -0.84534
C         -6.75192       -3.28667        0.60984
H         -6.91139       -4.36539        0.72723
C         -7.31956       -1.01134        1.17575
H         -7.92612       -0.29244        1.73971
C         -7.52711       -2.38177        1.33928
H         -8.29513       -2.74577        2.03196
C          0.58529       -5.11871       -1.86873
H         -0.32603       -5.72769       -1.98656
H          1.16192       -5.15436       -2.80823
H          1.19853       -5.54625       -1.05741
N         -0.00226       -2.65632       -1.29594
C          0.24441       -3.75984       -1.55577
86
Scheme S4, L=PPh3, Step 7 (minus CO), C44H39P2Pd, Electronic Energy: -2509.090545 a.u. Gibbs Free Energy: -2508.480017 a.u., Corrected Gibbs Free Energy: -2508.474824 a.u.
Pd         0.11726        0.61820       -1.12218
P          1.54994       -0.95904       -0.09469
C          2.76939       -1.59693       -1.30240
C          2.53098       -0.18241        1.23783
C          3.09151       -0.92179        2.29087
H          2.94138       -2.00650        2.34850
C          0.84507       -3.68249       -0.09975
H          1.29654       -3.72447       -1.09869
C          0.87110       -2.49027        0.63987
C          2.49977       -1.48400       -2.67245
H          1.58182       -0.97879       -3.00465
C          3.50160        1.83977        2.17060
H          3.65879        2.92338        2.12108
C          2.74144        1.20411        1.18959
H          2.29164        1.79210        0.37669
C          4.04999        1.09758        3.21816
H          4.63932        1.59715        3.99572
C          3.94020       -2.24520       -0.88338
H          4.16410       -2.34960        0.18598
C          3.84358       -0.28179        3.27592
H          4.27346       -0.86892        4.09549
C          3.38681       -2.01170       -3.61210
H          3.16476       -1.92125       -4.68154
C          0.27729       -2.46776        1.91188
H          0.30907       -1.55635        2.52056
C          0.23146       -4.82277        0.41775
H          0.21831       -5.74555       -0.17399
C          4.82992       -2.76205       -1.82376
H          5.74678       -3.25972       -1.48758
C          4.55394       -2.64774       -3.18849
H          5.25488       -3.05657       -3.92545
C         -0.34017       -3.60852        2.42362
H         -0.79653       -3.57499        3.42005
C         -0.37037       -4.78716        1.67615
H         -0.85650       -5.68271        2.08011
C          0.60481        2.55033       -2.28159
C         -0.75885        2.18870       -2.30103
H          1.51853        1.13769       -1.76930
H         -1.48415        2.74748       -1.69555
H         -1.16525        1.71089       -3.20332
C          2.41152        4.13069       -1.62163
C          1.16151        3.55662       -1.34866
C          0.48550        3.93878       -0.17748
C          1.04506        4.87167        0.69153
C          2.28983        5.44085        0.40646
C          2.97034        5.06843       -0.75368
H          2.95170        3.83152       -2.52842
H         -0.48646        3.49109        0.06560
H          0.50641        5.15539        1.60332
H          2.73030        6.17292        1.09321
H          3.94713        5.50915       -0.98428
H          1.18622        2.40217       -3.20210
P         -1.95068        0.06681       -0.07923
C         -1.69903        0.14943        1.73029
C         -3.34698        1.20712       -0.39034
C         -2.62886       -1.56445       -0.52534
C         -3.67277        2.23783        0.50103
H         -3.13856        2.33701        1.45409
C         -3.89572       -1.99553       -0.09559
H         -4.51809       -1.34632        0.53225
C         -1.88221       -2.38361       -1.38276
H         -0.90651       -2.03443       -1.74978
C         -0.68763        1.00645        2.19209
H         -0.09629        1.58767        1.46935
C         -2.43725       -0.59669        2.65821
H         -3.22386       -1.28321        2.32546
C         -4.68407        3.14739        0.18463
H         -4.93292        3.94681        0.89204
C         -1.14236        0.35271        4.47164
H         -0.92131        0.42254        5.54300
C         -3.61850       -4.06156       -1.32343
H         -4.00603       -5.03934       -1.63226
C         -0.41143        1.11045        3.55498
H          0.38549        1.78046        3.89947
C         -4.04360        1.10650       -1.60524
H         -3.79179        0.31147       -2.31959
C         -5.37740        3.03714       -1.02046
H         -6.17265        3.75059       -1.26508
C         -2.15558       -0.49600        4.02075
H         -2.73025       -1.09438        4.73724
C         -4.38015       -3.24220       -0.48547
H         -5.36655       -3.57321       -0.14093
C         -5.05506        2.01317       -1.91468
H         -5.59563        1.92011       -2.86368
C         -2.37471       -3.62731       -1.77994
H         -1.77977       -4.25971       -2.44929
70
Scheme S5, L=dppe, Step 6 (minus CO), C34H33P2Pd, Electronic Energy: -2124.741389 a.u. Gibbs Free Energy: -2124.246346 a.u., Corrected Gibbs Free Energy: -2124.240924 a.u.
Pd         0.05719        0.02709       -1.02806
C         -0.44002       -1.41580       -2.73054
C          0.94878       -1.25542       -2.50065
H         -1.30515       -0.19721       -1.90556
H         -0.85691       -0.94364       -3.63126
H          1.52030       -2.05106       -2.00521
H          1.52408       -0.62133       -3.18900
C         -2.48262       -2.84466       -2.77230
C         -1.21950       -2.57527       -2.22560
C         -0.74752       -3.39512       -1.18836
C         -1.51881       -4.45306       -0.71239
C         -2.77592       -4.71229       -1.26513
C         -3.25391       -3.90565       -2.29926
H         -2.86516       -2.20427       -3.57695
H          0.23095       -3.19842       -0.73422
H         -1.13526       -5.08154        0.10018
H         -3.38312       -5.54336       -0.88802
H         -4.23817       -4.10168       -2.74029
P          1.92984        0.37928        0.35596
P         -1.10139        1.31798        0.51132
C         -2.55131        0.50103        1.24984
C          1.48019        1.79477        1.45222
C          0.04312        1.64296        1.92579
C          2.12505       -1.03172        1.49961
C          3.59792        0.72512       -0.27360
C          3.32775       -1.27355        2.17970
H          4.19876       -0.62757        2.01081
C          4.20733       -0.23259       -1.10146
H          3.67835       -1.16316       -1.34403
C         -2.79160        2.95080       -0.96312
H         -3.26471        2.00811       -1.26922
C         -1.70736        2.93481       -0.06996
C         -3.35303        1.16980        2.18764
H         -3.13126        2.20917        2.46241
C          4.28727        1.90797        0.02761
H          3.83742        2.66948        0.67381
C          3.42319       -2.33912        3.07441
H          4.36789       -2.52449        3.59849
C         -2.85010       -0.82349        0.90386
H         -2.22314       -1.34463        0.16554
C          6.16626        1.16829       -1.30680
H          7.17047        1.34206       -1.71010
C         -4.43696        0.51581        2.77058
H         -5.06096        1.04259        3.50166
C         -1.11063        4.14656        0.30345
H         -0.26227        4.16611        0.99684
C          1.02309       -1.86844        1.73345
H          0.07958       -1.68384        1.19842
C          2.32181       -3.16708        3.30279
H          2.40245       -4.00497        4.00488
C          5.48510       -0.01326       -1.61006
H          5.95205       -0.76977       -2.25093
C          1.11995       -2.92892        2.63409
H          0.25205       -3.57563        2.80881
C         -3.27754        4.15752       -1.45985
H         -4.12942        4.15735       -2.14946
C         -3.93622       -1.47513        1.49011
H         -4.16482       -2.51074        1.21291
C         -4.72906       -0.80584        2.42302
H         -5.58395       -1.31569        2.88206
C          5.56567        2.12551       -0.48979
H          6.09646        3.05293       -0.24608
C         -1.59680        5.35348       -0.20378
H         -1.12309        6.29496        0.09699
C         -2.67928        5.36263       -1.08250
H         -3.05962        6.31201       -1.47646
H         -0.29052        2.51898        2.51050
H         -0.05586        0.76672        2.59419
H          2.17993        1.85524        2.30612
H          1.59957        2.71833        0.85538
6
Acetonitrile, C2H3N, Electronic Energy: -132.638178 a.u. Gibbs Free Energy: -132.617229 a.u., Corrected Gibbs Free Energy: -132.611431 a.u.
C         -1.16974       -0.00005       -0.00005
H         -1.55411        0.43275       -0.93841
H         -1.55431       -1.02896        0.09408
H         -1.55473        0.59608        0.84366
N          1.43559       -0.00006       -0.00014
C          0.27208        0.00014        0.00033
2
Silver chloride, AgCl, Electronic Energy: -607.219251 a.u. Gibbs Free Energy: -607.243006 a.u., Corrected Gibbs Free Energy: -607.239999 a.u.
Ag         0.00000        0.00000        0.63545
Cl         0.00000        0.00000       -1.75684
1
Silver ion, Ag+, Electronic Energy: -146.956032 a.u. Gibbs Free Energy: -146.972638 a.u., Corrected Gibbs Free Energy: -146.969619 a.u.
Ag         0.00000        0.00000        0.00000
2
Soddium chloride, NaCl, Electronic Energy: -622.392565 a.u. Gibbs Free Energy: -622.414415 a.u., Corrected Gibbs Free Energy: -622.411405 a.u.
Na         0.00000        0.00000       -1.48595
Cl         0.00000        0.00000        0.96150
1
Sodium ion, Na+, Electronic Energy: -162.140380 a.u.  Gibbs Free Energy: -162.154809 a.u., Corrected Gibbs Free Energy: -162.151790 a.u.
Na         0.00000        0.00000        0.00000
2
Carbon monoxide, CO, Electronic Energy: -113.204143 a.u. Gibbs Free Energy: -113.218196 a.u., Corrected Gibbs Free Energy: -113.215178 a.u.
C          0.00000        0.00000       -0.64731
O          0.00000        0.00000        0.48548



