Supporting Information for: electron ligands: Complex formation, oxidation and

Supporting Information for: The diverse reactions of PhI(OTf) 2 with common 2- electron ligands: Complex formation, oxidation and oxidative coupling Thomas P. Pell, Shannon A. Couchman, Sara Ibrahim, David J. D. Wilson, Brian J. Smith, Peter J. Barnard and Jason L. Dutton* Department of Chemistry, La Trobe Institute for Molecular Sciences, La Trobe University, Melbourne, Victoria, Australia, 3086 j.dutton@latrobe.edu.au S1

Table of Contents Cartesian coordinates and energies for optimized geometries... S3 Reaction energies... S14 S2

Cartesian coordinates and energies All calculations were performed at the ωb97xd/6-311++g(d,p) level using the GAUSSIAN-09 program. Cartesian coordinates are in Ångstrom, and energies are in hartree. Thermal energies, enthalpies and Gibbs energies are at 298.15 K and 1 atm. CO 3 F 3 S -, E(RwB97XD) = -961.543785089 16 0.928440 0.000009-0.000045 9-1.445596 0.761273 0.986868 9-1.446337-1.235277 0.165473 9-1.445726 0.474464-1.152943 8 1.242991-0.543286 1.320611 8 1.244811-0.872399-1.130096 8 1.244358 1.415192-0.189549 6-0.945565-0.000056-0.000264 Sum of electronic and zero-point Energies= -961.516228 Sum of electronic and thermal Energies= -961.509165 Sum of electronic and thermal Enthalpies= -961.508221 Sum of electronic and thermal Free Energies= -961.548539 G(benzene) = -961.591506 G(dichloromethane) = -961.620355 G(acetonitrile) = -961.627885 C 2 H 3 O -, E(RwB97XD) = -228.519764319 6 0.011342 0.209944 0.000000 6 0.000433-1.347816 0.000000 8 0.000433 0.750019 1.127972 8 0.000433 0.750019-1.127972 1-1.042997-1.685477 0.000000 1 0.482710-1.743796-0.898473 1 0.482710-1.743796 0.898473 Sum of electronic and zero-point Energies= -228.471380 Sum of electronic and thermal Energies= -228.466967 Sum of electronic and thermal Enthalpies= -228.466023 Sum of electronic and thermal Free Energies= -228.498938 G(benzene) = -228.577462 G(dichloromethane) = -228.613402 G(acetonitrile) = -228.622971 S3

C 5 H 8 N 2, E(RwB97XD) = -304.774569862 7-1.058708-0.122761 0.000022 6-0.675040 1.207613 0.000011 1-1.379694 2.023168-0.000014 6 0.675042 1.207606-0.000010 1 1.379694 2.023165 0.000009 6-0.000001-0.978239-0.000008 7 1.058707-0.122756-0.000024 6 2.437504-0.567274 0.000014 6-2.437501-0.567275-0.000006 1 2.432582-1.655415-0.000777 1 2.958032-0.208513 0.891443 1 2.958429-0.207237-0.890656 1-2.958090-0.208355-0.891340 1-2.432587-1.655406 0.000597 1-2.958389-0.207384 0.890756 Sum of electronic and zero-point Energies= -304.647159 Sum of electronic and thermal Energies= -304.640076 Sum of electronic and thermal Enthalpies= -304.639132 Sum of electronic and thermal Free Energies= -304.678577 G(benzene) = -304.778949 G(dichloromethane) = -304.783313 G(acetonitrile) = -304.784855 C 6 H 5 N, E(RwB97XD) = -248.255922696 7 0.000341-1.412886 0.000034 6-1.137379-0.719536 0.000035 1-2.052487-1.305283 0.000230 6-1.193507 0.669541-0.000056 1-2.150704 1.177001-0.000110 6 1.137722-0.719016-0.000117 1 2.053115-1.304339-0.000168 6 1.193187 0.670085 0.000095 1 2.150083 1.178102 0.000251 6-0.000336 1.379116-0.000030 1-0.000521 2.463573-0.000005 Sum of electronic and zero-point Energies= -248.166614 Sum of electronic and thermal Energies= -248.162357 Sum of electronic and thermal Enthalpies= -248.161412 Sum of electronic and thermal Free Energies= -248.194000 G(benzene) = -248.258466 G(dichloromethane) = -248.260887 G(acetonitrile) = -248.261701 S4

C H 5 I, E(RwB97XD) = -7151.29594584 6 0.000000 1.209320-1.248851 6 0.000000 1.201704-2.639303 6 0.000000 0.000000-3.336263 6 0.000000-1.201704-2.639303 6 0.000000-1.209320-1.248851 6 0.000000 0.000000-0.562813 53 0.000000 0.000000 1.551767 1 0.000000 2.148480-0.709955 1 0.000000 2.143867-3.175663 1 0.000000 0.000000-4.420138 1 0.000000-2.143867-3.175663 1 0.000000-2.148480-0.709955 Sum of electronic and zero-point Energies= -7151.205240 Sum of electronic and thermal Energies= -7151.199398 Sum of electronic and thermal Enthalpies= -7151.198453 Sum of electronic and thermal Free Energies= -7151.236301 G(benzene) = -7151.297573 G(dichloromethane) = -7151.299118 G(acetonitrile) = -7151.299642 S5

C 7 H 5 O 3 F 3 SI, E(RwB97XD) = -8112.36312194 53 0.726669-1.721967-0.130928 6 1.824054 0.017432 0.031247 6 1.918712 0.622921 1.289837 1 1.424890 0.205217 2.157952 6 2.652253 1.793259 1.383161 1 2.748266 2.287167 2.341969 6 3.258813 2.331048 0.250020 1 3.826886 3.249930 0.336653 6 3.146899 1.710995-0.993682 1 3.624709 2.142264-1.864449 6 2.426126 0.536809-1.121291 1 2.332645 0.046945-2.082552 16-2.031220-0.189333 0.477274 9-2.679488 2.323851 0.344188 9-2.554240 1.357915-1.584859 9-0.748087 1.870723-0.514335 8-3.334874-0.750305 0.389619 8-1.078859-0.998021-0.630180 8-1.267282-0.072934 1.688718 6-2.008004 1.480827-0.402115 Sum of electronic and zero-point Energies= -8112.243245 Sum of electronic and thermal Energies= -8112.228668 Sum of electronic and thermal Enthalpies= -8112.227724 Sum of electronic and thermal Free Energies= -8112.288204 G(benzene) = -8112.407172 G(dichloromethane) = -8112.435279 G(acetonitrile) = -8112.442926 S6

C 8 H 5 O 6 F 6 S 2 I, E(RwB97XD) = -9074.10319756 53-0.000110-1.233912-0.000072 6-0.000109 0.863592-0.000143 6-0.264876 1.519925 1.194214 1-0.492697 0.974680 2.100026 6-0.259144 2.907729 1.180110 1-0.464740 3.448010 2.096091 6 0.000123 3.594949-0.000145 1 0.000239 4.678842-0.000131 6 0.259229 2.907688-1.180413 1 0.464819 3.447932-2.096416 6 0.264729 1.519884-1.194510 1 0.492274 0.974622-2.100375 16 3.256082-0.899962-0.463415 9 3.094262 1.553938 0.491330 9 5.024874 1.015954-0.315014 9 4.406887 0.254301 1.609911 8 2.731082-0.423389-1.723824 8 4.245089-1.936741-0.414163 8 2.087961-1.205400 0.528665 6 3.995936 0.583103 0.397300 16-3.256535-0.900472 0.463020 9-5.024295 1.016524 0.315568 9-4.405781 0.256385-1.609758 9-3.093086 1.554350-0.489370 8-4.246218-1.936517 0.412421 8-2.088226-1.206049-0.528612 8-2.731760-0.425270 1.724035 6-3.995219 0.583806-0.396619 Sum of electronic and zero-point Energies= -9073.953960 Sum of electronic and thermal Energies= -9073.930759 Sum of electronic and thermal Enthalpies= -9073.929815 Sum of electronic and thermal Free Energies= -9074.011561 G(benzene) = -9074.111623 G(dichloromethane) = -9074.118979 G(acetonitrile) = -9074.121355 S7

C 8 H 8 O 2 I, E(RwB97XD) = -7379.4324162 53-0.533826-0.886198-0.009403 6 1.398976-0.116890-0.002647 6 2.018187 0.145719-1.226476 6 3.307466 0.654386-1.205120 6 3.947864 0.886193 0.009128 6 3.312918 0.612628 1.217416 6 2.023483 0.103984 1.226696 1 1.515809-0.036890-2.168288 1 3.821257 0.794083 2.156219 1 4.955545 1.284680 0.013738 1 3.811940 0.868228-2.139198 1 1.524815-0.110387 2.163785 8-1.345523 0.997753 0.011724 6-2.680871 0.826021 0.016154 8-3.122346-0.299167 0.009916 6-3.446991 2.108054 0.013809 1-4.498244 1.887783 0.182726 1-3.319484 2.590791-0.957735 1-3.062114 2.780959 0.780225 Sum of electronic and zero-point Energies= -7379.289647 Sum of electronic and thermal Energies= -7379.278501 Sum of electronic and thermal Enthalpies= -7379.277556 Sum of electronic and thermal Free Energies= -7379.329068 G(benzene) = -7379.472952 G(dichloromethane) = -7379.498130 G(acetonitrile) = -7379.504868 S8

C 8 H 11 O 2 I, E(RwB97XD) = -7608.18047255 53 0.005903-0.634443-0.000886 6-0.012013 1.486575-0.000849 6-0.875582 2.150818-0.859571 6-0.882413 3.540490-0.850444 6-0.037469 4.241551 0.001285 6 0.820605 3.554957 0.851666 6 0.839528 2.165345 0.858510 1-1.542949 1.602174-1.510377 1 1.480220 4.099192 1.517333 1-0.047916 5.325426 0.002370 1-1.551894 4.073389-1.515445 1 1.517047 1.627937 1.508279 8-2.148525-0.322700 0.065227 8 2.155333-0.287482-0.067092 6-2.777330-1.476844 0.132436 6 2.801552-1.431983-0.131133 8-2.192331-2.542852 0.142888 8 2.232398-2.506617-0.139896 6-4.277162-1.338648 0.189424 6 4.299223-1.271955-0.186870 1-4.731178-2.318260 0.324128 1-4.635626-0.889130-0.739130 1-4.557658-0.674039 1.008219 1 4.767198-2.244962-0.321635 1 4.571029-0.602828-1.004901 1 4.650241-0.818035 0.742401 Sum of electronic and zero-point Energies= -7607.986026 Sum of electronic and thermal Energies= -7607.969310 Sum of electronic and thermal Enthalpies= -7607.968366 Sum of electronic and thermal Free Energies= -7608.033400 G(benzene) = -7608.187108 G(dichloromethane) = -7608.193294 G(acetonitrile) = -7608.195373 S9

C 11 H 10 I 2+,E(RwB97XD) = -7398.8458509 53-0.042848-1.311748-0.042320 6-1.624325 0.010845 0.008346 6-3.248470 1.210012 1.269905 1-3.685742 1.506975 2.215383 6-2.145970 0.375754 1.260669 1-1.723666 0.011224 2.189191 6-3.801491 1.656072 0.067770 1-4.669557 2.305231 0.091271 7 1.645174-0.006176-0.006854 6 2.119933 0.485267-1.177590 1 1.612699 0.197710-2.089792 6 3.219783 1.313436-1.172616 1 3.590790 1.698076-2.114703 6-3.267803 1.273067-1.164336 1-3.719399 1.618661-2.086244 6-2.165950 0.439436-1.215148 1-1.759638 0.122016-2.167888 6 2.224697 0.281171 1.184600 1 1.795645-0.160051 2.075283 6 3.327344 1.104792 1.224567 1 3.783028 1.323232 2.182515 6 3.833411 1.628125 0.037419 1 4.703603 2.274924 0.054410 Sum of electronic and zero-point Energies= -7398.664094 Sum of electronic and thermal Energies= -7398.652488 Sum of electronic and thermal Enthalpies= -7398.651544 Sum of electronic and thermal Free Energies= -7398.705020 G(benzene) = -7398.989025 G(dichloromethane) = -7399.075618 G(acetonitrile) = -7399.098476 S10

C 12 H 16 N 2+ 4,E(RwB97XD) = -609.099179066 7 1.518362 0.813320 0.721741 6 0.730613 0.000010-0.000005 7 1.518106-0.813576-0.721806 6 2.824328-0.510365-0.450942 6 2.824492 0.509844 0.450713 6 1.075403 1.875964 1.634635 1 0.005026 1.777489 1.808311 1 1.603796 1.770748 2.580922 1 1.292988 2.847381 1.191462 6 1.074728-1.875856-1.634890 1 0.004162-1.777782-1.807533 1 1.293138-2.847434-1.192488 1 1.602166-1.769939-2.581545 1 3.644970 1.034339 0.914665 1 3.644610-1.035141-0.914823 7-1.518218-0.813467 0.721723 6-0.730599 0.000117 0.000137 7-1.518194 0.813537-0.721683 6-2.824388 0.510124-0.450862 6-2.824408-0.510158 0.450716 6-1.075179-1.875784 1.634956 1-0.004348-1.778750 1.806639 1-1.601698-1.768868 2.582028 1-1.294967-2.847316 1.193089 6-1.075026 1.876163-1.634494 1-0.004655 1.777548-1.808127 1-1.292500 2.847599-1.191251 1-1.603355 1.771092-2.580800 1-3.644722 1.034764-0.914776 1-3.644785-1.034795 0.914617 Sum of electronic and zero-point Energies= -608.835826 Sum of electronic and thermal Energies= -608.821521 Sum of electronic and thermal Enthalpies= -608.820577 Sum of electronic and thermal Free Energies= -608.877485 G(benzene) = -609.241103 G(dichloromethane) = -609.325381 G(acetonitrile) = -609.347239 S11

C 16 H 15 N 2 I 2+,E(RwB97XD) = -7647.19770165 53 0.000000-0.825901-0.000023 7-2.268563-0.759504-0.018797 6 0.000000 1.288601-0.000012 6-2.926750-1.597393 0.802309 1-2.331182-2.217224 1.463276 6-4.305964-1.658501 0.799628 1-4.810378-2.340539 1.471824 6-0.371799 3.332421 1.151229 1-0.657063 3.874339 2.044900 6-0.373720 1.942522 1.168872 1-0.659268 1.406152 2.065788 6-2.940077 0.041267-0.864901 1-2.353581 0.696887-1.497593 6-4.319169 0.025642-0.911734 1-4.836103 0.678741-1.602861 6-5.014098-0.836829-0.070056 1-6.097124-0.868536-0.092469 6 0.000006 4.020181 0.000008 1 0.000010 5.103752 0.000016 7 2.268561-0.759509 0.018780 6 2.926769-1.597604-0.802099 1 2.331219-2.217602-1.462925 6 4.305983-1.658715-0.799363 1 4.810415-2.340926-1.471371 6 0.371808 3.332436-1.151223 1 0.657074 3.874366-2.044886 6 0.373723 1.942537-1.168886 1 0.659266 1.406179-2.065811 6 2.940053 0.041472 0.864702 1 2.353543 0.697253 1.497214 6 4.319143 0.025858 0.911576 1 4.836059 0.679131 1.602552 6 5.014095-0.836827 0.070135 1 6.097119-0.868530 0.092588 Sum of electronic and zero-point Energies= -7646.923521 Sum of electronic and thermal Energies= -7646.906338 Sum of electronic and thermal Enthalpies= -7646.905393 Sum of electronic and thermal Free Energies= -7646.972456 G(benzene) = -7647.322830 G(dichloromethane) = -7647.397749 G(acetonitrile) = -7647.417259 S12

C 16 H 22 N 4 I 2+,E(RwB97XD) = -7760.3333402 53 0.000000 0.000000 0.844672 6 0.000000 0.000000-1.292077 6 0.000000 0.000000-4.032425 1 0.000000 0.000000-5.115828 6 0.874218 0.851114-1.949878 6-0.874218-0.851114-1.949878 1 1.551408 1.505424-1.413965 1-1.551408-1.505424-1.413965 6 0.863996 0.842847-3.341215 6-0.863996-0.842847-3.341215 1 1.541446 1.492851-3.881934 1-1.541446-1.492851-3.881934 6-0.274640 2.282962 0.662496 6 0.274640-2.282962 0.662496 7 0.500210 3.213043 1.247955 7-0.500210-3.213043 1.247955 7-1.259694 2.944850 0.031767 7 1.259694-2.944850 0.031767 6-1.101510 4.299662 0.215758 6 1.101510-4.299662 0.215758 6 0.000000 4.468363 0.984003 6 0.000000-4.468363 0.984003 6 1.663787 2.963725 2.100884 6-1.663787-2.963725 2.100884 6-2.317732 2.347349-0.781901 6 2.317732-2.347349-0.781901 1 0.462516 5.364341 1.363909 1-0.462516-5.364341 1.363909 1-1.780681 5.021511-0.206941 1 1.780681-5.021511-0.206941 1-1.345749-2.744182 3.120485 1 1.345749 2.744182 3.120485 1-2.287567-3.855458 2.105056 1 2.287567 3.855458 2.105056 1-2.248247-2.136049 1.701927 1 2.248247 2.136049 1.701927 1-2.731106 1.477726-0.272388 1 2.731106-1.477726-0.272388 1-3.109758 3.082118-0.910537 1 3.109758-3.082118-0.910537 1-1.923108 2.059514-1.756920 1 1.923108-2.059514-1.756920 Sum of electronic and zero-point Energies= -7759.980609 Sum of electronic and thermal Energies= -7759.958168 Sum of electronic and thermal Enthalpies= -7759.957224 Sum of electronic and thermal Free Energies= -7760.035022 G(benzene) = -7760.454930 G(dichloromethane) = -7760.527180 G(acetonitrile) = -7760.545898 S13

Reaction energies And energies are in kj mol -1. Reaction enthalpies and Gibbs reaction energies are at 298.15 K and 1 atm. E 865.8 E 0 869.6 H 298 868.5 866.5 (benzene) 322.7 (dichloromethane) 6.5 (acetonitrile) -73.7 E 445.4 E 0 458.8 H 298 453.2 414.4 (benzene) -167.9 (dichloromethane) -502.5 (acetonitrile) -586.5 E 607.6 E 0 617.6 H 298 615.5 621.2 (benzene) 96.5 (dichloromethane) -202.4 (acetonitrile) -276.8 S14

E 1194.8 E 0 1189.3 H 298 1191.3 1184.3 (benzene) 583.6 (dichloromethane) 227.1 (acetonitrile) 135.4 E 251.9 E 0 243.7 H 298 242.7 192.8 (benzene) 138.7 (dichloromethane) 101.7 (acetonitrile) 90.8 E 599.4 E 0 590.7 H 298 590.2 539.3 (benzene) 298.8 (dichloromethane) 154.5 (acetonitrile) 117.2 S15

E 515.4 E 0 510.6 H 298 509.2 459.0 (benzene) 240.2 (dichloromethane) 109.9 (acetonitrile) 76.3 E 936.6 E 0 937.2 H 298 938.2 939.0 (benzene) 357.1 (dichloromethane) 17.8 (acetonitrile) -68.0 S16