Supporting Information
Theoretical study on the mechanism of iridium-catalyzed γ-functionalization of primary alkyl C-H bonds
Zhe Li*1, Miaoren Xia2, Russell J. Boyd1
1. Department of Chemistry, Dalhousie University, Halifax Nova Scotia B3H 4R2, Canada;
2. CAS Key Laboratory of Nuclear Radiation and Nuclear Energy Techniques, and Multidisciplinary Initiative Center, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Email address:
Table of content
Geometry optimization in THF solution 4
Full citation of Gaussian 09 4
Cartesian coordinates, energies and negative frequencies: Me4phen 4
Cartesian coordinates, energies and negative frequencies: phen 5
Cartesian coordinates, energies and negative frequencies: cod 6
Cartesian coordinates, energies and negative frequencies: coe 6
Cartesian coordinates, energies and negative frequencies: HSi(OR)Et2 7
Cartesian coordinates, energies and negative frequencies: HSi(OMe)Et2 8
Cartesian coordinates, energies and negative frequencies: product 9
Cartesian coordinates, energies and negative frequencies: THF 10
Cartesian coordinates, energies and negative frequencies: norbornene 11
Cartesian coordinates, energies and negative frequencies: 1 11
Cartesian coordinates, energies and negative frequencies: 2 13
Cartesian coordinates, energies and negative frequencies: 3 14
Cartesian coordinates, energies and negative frequencies: 4 16
Cartesian coordinates, energies and negative frequencies: 2 19
Cartesian coordinates, energies and negative frequencies: 6 21
Cartesian coordinates, energies and negative frequencies: TS6-7a 23
Cartesian coordinates, energies and negative frequencies: 7a 25
Cartesian coordinates, energies and negative frequencies: 7b 26
Cartesian coordinates, energies and negative frequencies: 8 28
Cartesian coordinates, energies and negative frequencies: TS8-9 30
Cartesian coordinates, energies and negative frequencies: 9 32
Cartesian coordinates, energies and negative frequencies: TS9-10 35
Cartesian coordinates, energies and negative frequencies: 10a 37
Cartesian coordinates, energies and negative frequencies: 10b 38
Cartesian coordinates, energies and negative frequencies: TS7b-11a 40
Cartesian coordinates, energies and negative frequencies: 11a 42
Cartesian coordinates, energies and negative frequencies: 11b 45
Cartesian coordinates, energies and negative frequencies: 12 47
Cartesian coordinates, energies and negative frequencies: TS12-13 49
Cartesian coordinates, energies and negative frequencies: 13a 52
Cartesian coordinates, energies and negative frequencies: 13b 55
Cartesian coordinates, energies and negative frequencies: TS13b-14 57
Cartesian coordinates, energies and negative frequencies: 14 61
Cartesian coordinates, energies and negative frequencies: TS14-15 64
Cartesian coordinates, energies and negative frequencies: 15 67
Cartesian coordinates, energies and negative frequencies: TS15-16 70
Cartesian coordinates, energies and negative frequencies: 16a 73
Cartesian coordinates, energies and negative frequencies: TS16a-b 75
Cartesian coordinates, energies and negative frequencies: 16b 78
Cartesian coordinates, energies and negative frequencies: TS16b-11b 81
Cartesian coordinates, energies and negative frequencies: TS13-17 84
Cartesian coordinates, energies and negative frequencies: 17 87
Cartesian coordinates, energies and negative frequencies: TS17-18 89
Cartesian coordinates, energies and negative frequencies: TS17-21 92
Cartesian coordinates, energies and negative frequencies: 18 95
Cartesian coordinates, energies and negative frequencies: 20 97
Cartesian coordinates, energies and negative frequencies: TS20-8b 100
Cartesian coordinates, energies and negative frequencies: 8b 103
Optimization in THF solution: 11a 104
Optimization in THF solution: 11b 107
Optimization in THF solution: TS9-10 109
Optimization in THF solution: TS13b-14 111
Optimization in THF solution: HSi(OMe)Et2 114
Optimization in THF solution: HSi(OR)Et2 115
Optimization in THF solution: norbornene 116
Geometry optimization in THF solution
Geometry optimizations in THF solution were performed for key species (11a, TS9-10, and TS13b-14) using polarizable continuum model (PCM) at the level of B3LYP/BS1. The single point energies were calculated by M06/BS2 method in THF solution using the CPCM method. The Gibbs energy was obtained by adding TCG to the single point energy.
Full citation of Gaussian 09
Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
Cartesian coordinates, energies and negative frequencies: Me4phen
7 1.368236 -1.780936 0.000134
6 0.729344 -0.589037 -0.000003
6 2.686437 -1.767072 0.000127
6 1.433437 0.647854 -0.000064
6 -0.729344 -0.589039 -0.000068
6 3.499792 -0.608290 0.000007
1 3.172419 -2.744328 0.000207
6 2.859487 0.628103 -0.000039
6 0.681710 1.869887 -0.000118
6 -1.433439 0.647851 -0.000027
7 -1.368238 -1.780939 -0.000137
6 5.002519 -0.769746 0.000004
6 3.634210 1.925912 0.000029
6 -0.681717 1.869888 -0.000075
1 1.210771 2.817183 -0.000194
6 -2.859490 0.628101 0.000032
6 -2.686436 -1.767074 -0.000131
1 5.466706 -0.312020 -0.882303
1 5.466504 -0.313616 0.883267
1 5.273849 -1.830214 -0.000914
1 3.395092 2.533546 0.881736
1 4.712255 1.756819 0.000228
1 3.395382 2.533519 -0.881775
1 -1.210779 2.817183 -0.000097
6 -3.499793 -0.608291 -0.000016
6 -3.634200 1.925918 0.000154
1 -3.172419 -2.744327 -0.000218
6 -5.002521 -0.769746 0.000066
1 -3.394872 2.533669 0.881720
1 -3.395569 2.533409 -0.881788
1 -4.712249 1.756845 0.000603
1 -5.466528 -0.312990 0.882983
1 -5.466683 -0.312649 -0.882590
1 -5.273850 -1.830215 -0.000112
Zero-point correction= 0.282749 (Hartree/Particle)
Thermal correction to Energy= 0.298619
Thermal correction to Enthalpy= 0.299563
Thermal correction to Gibbs Free Energy= 0.240271
Sum of electronic and zero-point Energies= -728.580880
Sum of electronic and thermal Energies= -728.565011
Sum of electronic and thermal Enthalpies= -728.564067
Sum of electronic and thermal Free Energies= -728.623359
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: phen
7 -1.381538 -1.563427 0.000321
7 1.381621 -1.563462 -0.000370
6 -0.729535 -0.377862 0.000029
6 -2.704259 -1.549120 0.000164
6 0.729624 -0.378056 -0.000012
6 2.704530 -1.548997 -0.000472
6 -1.417329 0.870646 -0.000175
6 -3.483223 -0.373154 0.000050
1 -3.194187 -2.522702 0.000908
6 1.417317 0.870887 0.000140
6 3.483218 -0.373126 0.000184
1 3.194527 -2.522502 -0.000408
6 -0.680721 2.101972 -0.000153
6 -2.829833 0.841506 -0.000240
1 -4.567421 -0.434355 0.000111
6 2.829663 0.841652 0.000303
6 0.680456 2.102020 0.000063
1 4.567456 -0.433636 0.000504
1 -1.234833 3.037684 -0.000341
1 -3.383281 1.777831 -0.000448
1 3.383452 1.777808 0.000553
1 1.234261 3.037888 0.000178
Zero-point correction= 0.171077 (Hartree/Particle)
Thermal correction to Energy= 0.180224
Thermal correction to Enthalpy= 0.181168
Thermal correction to Gibbs Free Energy= 0.136421
Sum of electronic and zero-point Energies= -571.427152
Sum of electronic and thermal Energies= -571.418006
Sum of electronic and thermal Enthalpies= -571.417061
Sum of electronic and thermal Free Energies= -571.461808
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: cod
6 -0.007930 -1.704606 -0.218465
6 1.215364 -1.235914 -0.495421
6 1.923400 0.011064 -0.023982
6 1.082850 1.107605 0.665580
6 0.007932 1.704611 -0.218434
6 -1.215354 1.235920 -0.495430
6 -1.923399 -0.011074 -0.024045
6 -1.082862 -1.107609 0.665538
1 -0.291455 -2.634683 -0.712295
1 1.822215 -1.841193 -1.171212
1 2.741144 -0.283398 0.653881
1 2.425446 0.456105 -0.896051
1 0.665530 0.724345 1.600164
1 1.771188 1.910006 0.959599
1 0.291455 2.634707 -0.712228
1 -1.822193 1.841219 -1.171214
1 -2.425398 -0.456108 -0.896145
1 -2.741179 0.283372 0.653782
1 -1.771199 -1.910014 0.959549
1 -0.665557 -0.724343 1.600125
Zero-point correction= 0.181197 (Hartree/Particle)
Thermal correction to Energy= 0.188621
Thermal correction to Enthalpy= 0.189565
Thermal correction to Gibbs Free Energy= 0.149671
Sum of electronic and zero-point Energies= -311.843268
Sum of electronic and thermal Energies= -311.835844
Sum of electronic and thermal Enthalpies= -311.834900
Sum of electronic and thermal Free Energies= -311.874794
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: coe
6 1.655135 -0.700633 0.392061
6 1.730631 0.780822 -0.047679
6 -1.392143 -0.836231 0.650744
6 0.492606 1.659475 0.231095
6 -1.865602 0.513427 0.060241
6 -0.773828 1.366762 -0.611899
1 1.350606 -0.734318 1.447353
1 1.964107 0.825856 -1.120905
1 0.249319 1.617550 1.303367
1 -0.799118 -0.636727 1.551808
1 -2.333317 1.091724 0.869687
1 2.670223 -1.116211 0.358037
1 2.586656 1.236850 0.469380
1 -2.273294 -1.401071 0.981847
1 0.797856 2.697206 0.042854
1 -2.657087 0.327648 -0.679184
1 -1.241371 2.320418 -0.890550
1 -0.473487 0.894285 -1.555128
6 0.746999 -1.573779 -0.445652
1 1.232057 -2.165217 -1.222452
6 -0.583181 -1.652847 -0.321245
1 -1.136847 -2.299965 -1.002110
Zero-point correction= 0.205176 (Hartree/Particle)
Thermal correction to Energy= 0.212851
Thermal correction to Enthalpy= 0.213795
Thermal correction to Gibbs Free Energy= 0.173675
Sum of electronic and zero-point Energies= -313.053672
Sum of electronic and thermal Energies= -313.045997
Sum of electronic and thermal Enthalpies= -313.045053
Sum of electronic and thermal Free Energies= -313.085173
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: HSi(OR)Et2
6 -3.913241 -1.848342 -0.012242
1 -4.032549 -1.938360 1.074562
1 -3.938458 -2.859512 -0.434517
1 -4.785735 -1.304977 -0.396030
6 -2.608187 -1.127210 -0.367250
1 -1.756509 -1.712289 -0.001747
1 -2.505546 -1.076091 -1.461416
6 -2.533579 0.288464 0.215755
1 -3.409891 0.862864 -0.117873
1 -2.588922 0.239150 1.312374
6 -1.275148 1.078272 -0.167735
1 -1.199762 1.110657 -1.267950
6 -1.338322 2.519579 0.358396
1 -2.277321 2.967887 0.006045
1 -1.397524 2.481608 1.454354
6 -0.161551 3.400330 -0.068842
1 0.783182 3.018952 0.330834
1 -0.072945 3.445394 -1.161722
1 -0.286864 4.425856 0.296631
8 -0.117938 0.425197 0.365278
14 1.226342 -0.136325 -0.452018
1 1.194145 0.398347 -1.852022
6 2.762737 0.501093 0.447749
1 2.694879 0.204279 1.503713
1 2.727186 1.598905 0.447442
6 1.229353 -2.027168 -0.537748
1 2.099453 -2.337150 -1.135588
1 0.349077 -2.346709 -1.112181
6 1.248638 -2.740124 0.826868
1 1.230345 -3.830975 0.713165
1 2.148008 -2.487025 1.401373
1 0.382978 -2.456023 1.436242
6 4.100047 0.022885 -0.148116
1 4.202053 0.316763 -1.200105
1 4.954897 0.447235 0.392303
1 4.196068 -1.068482 -0.102879
Zero-point correction= 0.326312 (Hartree/Particle)
Thermal correction to Energy= 0.344148
Thermal correction to Enthalpy= 0.345092
Thermal correction to Gibbs Free Energy= 0.278966
Sum of electronic and zero-point Energies= -759.967625
Sum of electronic and thermal Energies= -759.949789
Sum of electronic and thermal Enthalpies= -759.948845
Sum of electronic and thermal Free Energies= -760.014971
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: HSi(OMe)Et2
6 -2.703797 -0.797190 -0.008679
1 -2.813712 -1.279843 0.973555
8 -1.373542 -0.875027 -0.488262
14 -0.044835 -0.377145 0.398037
1 -0.067698 -1.055039 1.735863
6 1.465222 -0.939082 -0.581320
1 1.443584 -0.459167 -1.569103
1 1.357649 -2.015349 -0.771484
6 -0.065755 1.493286 0.696933
1 0.789513 1.743328 1.342127
1 -0.957170 1.742875 1.290473
6 -0.032833 2.353012 -0.580439
1 -0.065800 3.424404 -0.347956
1 0.878957 2.172398 -1.161991
1 -0.883813 2.129404 -1.233943
6 2.811214 -0.658945 0.113094
1 2.866100 -1.142716 1.095885
1 3.653943 -1.031515 -0.481449
1 2.972257 0.414880 0.267576
1 -3.046336 0.244206 0.076936
1 -3.355762 -1.314109 -0.720437
Zero-point correction= 0.183783 (Hartree/Particle)
Thermal correction to Energy= 0.195040
Thermal correction to Enthalpy= 0.195984
Thermal correction to Gibbs Free Energy= 0.146281
Sum of electronic and zero-point Energies= -563.536544
Sum of electronic and thermal Energies= -563.525287
Sum of electronic and thermal Enthalpies= -563.524343
Sum of electronic and thermal Free Energies= -563.574046
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: product
6 1.302669 0.285855 0.360509
6 -0.457939 -1.066796 1.531604
6 1.016042 -1.064395 1.054558
1 1.434330 1.061423 1.134277
1 -0.550876 -0.558854 2.500852
1 -0.842489 -2.083839 1.663024
1 1.721108 -1.238386 1.876408
1 1.168103 -1.869770 0.322124
14 -1.285101 -0.043925 0.157107
8 0.147812 0.634510 -0.427908
6 -2.459170 1.295032 0.798136
1 -3.321442 0.806913 1.276543
1 -1.941175 1.835908 1.602792
6 -2.947686 2.294411 -0.267340
1 -3.603548 3.058850 0.167325
1 -2.105210 2.811146 -0.740592
1 -3.513510 1.793292 -1.062054
6 -2.091905 -1.077706 -1.208233
1 -2.233077 -0.441182 -2.092974
1 -1.368320 -1.846616 -1.513113
6 -3.427854 -1.739780 -0.820909
1 -4.190648 -0.993584 -0.568265
1 -3.828204 -2.349776 -1.639808
1 -3.315414 -2.398553 0.049352
6 2.529928 0.290456 -0.550265
1 2.554002 1.254491 -1.075240
1 2.393271 -0.480090 -1.322359
6 3.860595 0.071391 0.182854
1 3.858980 -0.910042 0.675998
1 3.962065 0.816422 0.985203
6 5.071861 0.163163 -0.752094
1 6.009985 0.004017 -0.208082
1 5.015063 -0.590106 -1.547442
1 5.126685 1.147417 -1.233126
Zero-point correction= 0.307099 (Hartree/Particle)
Thermal correction to Energy= 0.323239
Thermal correction to Enthalpy= 0.324183
Thermal correction to Gibbs Free Energy= 0.262796
Sum of electronic and zero-point Energies= -758.789224
Sum of electronic and thermal Energies= -758.773084
Sum of electronic and thermal Enthalpies= -758.772139
Sum of electronic and thermal Free Energies= -758.833526
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: THF
8 0.000039 -1.203739 -0.294765
6 -1.132055 -0.471677 0.157265
6 1.132122 -0.471588 0.157154
6 -0.777379 1.017325 -0.050146
1 -1.999323 -0.808237 -0.417527
1 -1.320417 -0.679986 1.224538
6 0.777267 1.017426 -0.049998
1 1.320694 -0.680014 1.224366
1 1.999329 -0.807981 -0.417829
1 -1.200115 1.649601 0.736900
1 -1.164089 1.378824 -1.007801
1 1.199752 1.649557 0.737300
1 1.164126 1.379238 -1.007475
Zero-point correction= 0.117628 (Hartree/Particle)
Thermal correction to Energy= 0.122568
Thermal correction to Enthalpy= 0.123512
Thermal correction to Gibbs Free Energy= 0.088540
Sum of electronic and zero-point Energies= -232.327772
Sum of electronic and thermal Energies= -232.322833
Sum of electronic and thermal Enthalpies= -232.321888
Sum of electronic and thermal Free Energies= -232.356861
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: norbornene
6 1.279519 0.669765 -0.507773
6 0.088421 1.128493 0.322988
6 0.087287 -1.128537 0.323105
6 1.278562 -0.670998 -0.508116
1 1.921621 1.327914 -1.085403
1 1.919807 -1.329769 -1.085990
6 0.041481 0.000064 1.380781
1 -0.877818 0.000576 1.980124
1 0.912919 -0.000341 2.043156
6 -1.190867 0.781383 -0.516474
1 -2.088275 1.178813 -0.028250
1 -1.145895 1.207071 -1.523366
6 -1.191849 -0.780363 -0.516080
1 -2.089598 -1.176500 -0.027424
1 -1.147625 -1.206582 -1.522777
1 0.120777 2.157587 0.689553
1 0.118761 -2.157614 0.689793
Zero-point correction= 0.153715 (Hartree/Particle)
Thermal correction to Energy= 0.158914
Thermal correction to Enthalpy= 0.159858
Thermal correction to Gibbs Free Energy= 0.125196
Sum of electronic and zero-point Energies= -272.568979
Sum of electronic and thermal Energies= -272.563779
Sum of electronic and thermal Enthalpies= -272.562835
Sum of electronic and thermal Free Energies= -272.597497
No negative Frequencies
Cartesian coordinates, energies and negative frequencies: 1
77 -1.576986 -0.005461 -0.202864
8 0.002862 -1.260308 -0.754189
6 0.004044 -2.673405 -0.707604
1 -0.944913 -3.056652 -1.099344
1 0.141002 -3.055933 0.313563
6 -2.779207 1.352403 0.900258
1 -2.153207 2.170830 1.258805