Supplemental File for

Synthesis, Reactivity and Photochemistry of π-Conjugated Tellurophenes

by Elisa Iolanda Carrera Boutzis

Density Functional Theory (DFT) Data

Density Functional Theory Data for Chapter 2……………………………………………………4 Geometry coordinates for IIT’…………………………………………………………………4 Geometry coordinates for IIT-Br2’…………………………………………………………....6 Geometry coordinates for IIT-Cl2’…………………………………………………………….8

Density Functional Theory Data for Chapter 3………………………………....………………..10 Geometry coordinates for PT (B3LYP, 6-31g(d)/LANL2DZ)……………………………….10 Geometry coordinates for PT-Br2 (B3LYP, 6-31g(d)/LANL2DZ)…………………………..11 Geometry coordinates for PT-Cl2 (B3LYP, 6-31g(d)/LANL2DZ)…………………………..12 Geometry coordinates for PT-F2 (B3LYP, 6-31g(d)/LANL2DZ)…………………………....13 Geometry coordinates for PT (B3LYP, 6-31g(d)/SDD)………………………………………14 Geometry coordinates for PT-Br2 (B3LYP, 6-31g(d)/SDD)………………………………....15 Geometry coordinates for PT (CAM-B3LYP, 6-31g(d)/SDD)..……………..…………….…16 Geometry coordinates for PT-Br2 (CAM-B3LYP, 6-31g(d)/SDD)……………………….….17

Density Functional Theory Data for Chapter 4………………………………....…………….…..18 Geometry Coordinates for PT-R Structures………………………………………………….…..18

PT (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) …………………………………….….18 PT-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………....19 PT-tBu (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)…………………………….……...20 PT-tBu-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)………………………….…....22 PT-OtBu (gas phase, B3LYP, 6-311+g(d)/LANL2DZ).……………………………....…24 PT-OtBu-Br2 (gas phase, B3LYP, 6-311+g(d)/L.ANL2DZ).……………………….…...26 PT-NEt2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ).………………………….……....28 PT-NEt2-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ).………………………….….30 PT-CN (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)………………………………….....32 PT-CN-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)……………………………….33 PT-CF3 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ).………………………………..….34 PT-CF3 triplet state optimization (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…...…35 PT-CF3-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)……………………………….36 PT-C6F5 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………..37

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PT-C6F5-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) ……………………………..38 PT-NO2-NBu2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)……………………………39 PT-NO2-NBu2-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ)……………………….41

Geometry Coordinates for Structures Used in Mechanistic Study…………………………….43 Reactants PT and Br2 (gas phase B3LYP, 6-311g(d)/LANL2DZ)………………………43 Int1 (gas phase, B3LYP, 6-311g(d)/LANL2DZ)………………………………………....44 TS1 (gas phase, B3LYP, 6-311g(d)/LANL2DZ)………………………………………....45 Int2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ)………………………………………....46 TS2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ)………………………………………....47 Product PT-Br2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ)…………………………….48 Reactants PT and Br2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…………………49 Int1 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………….50 TS1 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………….51 Int2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………….52 TS2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ)…………………………………….53 Product PT-Br2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) ……………………….54 Figure S1 IRC path for gas-phase optimized structure of TS1-2 and the associated

geometries. The “reactant” and “product” geometries from IRC optimize to the geometries of Int1 and Int2, respectively, in a few steps……………………………...55

Figure S2 IRC path for gas-phase optimized structure of TS2-P and the associated geometries. The “reactant” and “product” geometries from IRC optimize to the geometries of Int2 and PT-Br2, respectively, in a few steps…………………………..56

Density Functional Theory Data for Chapter 5…………………………………………………...57 Geometry Coordinates and Energies for Minimum Energy Structures………………………..57

PT…………………………………………………………………………………………57 PT-O………………………………………………………………………………………58 PT-O2………………………………………………………………………………….…..59 IntA……………………………………………………………………………………….60 IntB………………………………………………………………………………………..61 IntC……………………………………………………………………………………….62 IntC’ + TeO2 + CBA (optimized from TSA-C IRC product structure)……………………63 IntC’ + TeO2 + CBA (optimized from TSPTO2-C IRC product structure)………………...64 IntD……………………………………………………………………………………….65 (Z)-ED…………………………………………………………………………………….66 TeO2………………………………………………………………………………………66 MCPBA…………………………………………………………………………………...67 CBA……………………………………………………………………………………….67

Geometry Coordinates and Energies for Transition State Structures………………………….68 TSPT-PTO…………………………………………………………………………………...68 TSPTO-PTO2………………………………………………………………………………...69

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TSPTO2-C…………………………………………………………………………………..70 TSC’-(Z)-ED…………………………………………………………………………………71 TSPTO-A……………………………………………………………………………………72 TSA-C………………………………………………………………………………………73 TSA-B………………………………………………………………………………………74 TSB-D………………………………………………………………………………………75 TSC-D………………………………………………………………………………………76

Figure S3. IRC path leading from TSPT-PTO to the connected reactant and product geometries. These structures resemble the expected reactants (PT + MCPBA) and products (PT-O + CBA)…………………………………………………………………..77

Figure S4. IRC path leading from TSPTO-PTO2 to the connected reactant and product geometries. These structures resemble the expected reactants (PT-O + MCPBA) and products (PT-O2 + CBA)………………………………………………………………….78

Figure S5. IRC path leading from TSPTO2-C to the connected reactant and product geometries. The structure obtained in the reverse direction resembles the expected reactants (PT-O2 + MCPBA), while the forward structure resembles a ring-opened product and CBA. Optimization from this structure leads to the diphenylfuran (IntC’ + TeO2 + CBA)……………………………………………………………………79

Figure S6. IRC path leading from TSC’-(Z)-ED to the connected reactant and product geometries. These structures resemble the expected reactants (IntC’ + MCPBA) and products ((Z)-ED + CBA).………………………………………………………………...80

Figure S7. IRC path leading from TSPTO-A to the connected reactant and product geometries. These structures resemble the expected reactants (PT-O + MCPBA) and products (IntA + CBA).…………………………………………………………………..81

Figure S8. IRC path leading from TSA-C to the connected reactant and product geometries. The structure obtained in the reverse direction resembles the expected reactants (IntA + MCPBA), while the forward structure resembles a ring-opened product and CBA. Optimization from this structure leads to the diphenylfuran (IntC’ + TeO2 + CBA)……………………………………………………………………82

Figure S9. IRC path leading from TSA-B to the connected reactant and product geometries. These structures resemble the expected reactants (IntA + MCPBA) and products (IntB + CBA). …………………………………………………………………..83

Figure S10. IRC path leading from TSB-D to the connected reactant and product geometries. These structures resemble the expected reactants (IntB + MCPBA) and products (IntD + CBA).…………………………………………………………………..84

Figure S11. Relative energy diagram for Paths A (green), B’ (blue) and C’ (red)……………85

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Density Functional Theory Data for Chapter 2 Geometry coordinates for IIT’: C -1.04356 -0.94437 -3.5563 C 0.26101 -1.00207 -3.97108 C 0.84884 0.13579 -4.60599 C 0.09382 1.26519 -4.78544 H 0.85541 -1.89841 -3.80606 H 1.87849 0.09767 -4.95468 Te -1.83943 0.95689 -4.00265 C -1.82004 -2.01649 -2.92695 C -2.91315 -1.72274 -2.08743 C -1.49028 -3.3663 -3.16007 C -3.65836 -2.74118 -1.48743 H -3.1825 -0.69489 -1.90019 C -2.19029 -4.40637 -2.54715 H -0.68145 -3.60648 -3.84295 C -3.25431 -4.08123 -1.71679 C -4.78744 -2.77978 -0.54165 H -1.91319 -5.44027 -2.72714 N -4.05724 -4.9544 -0.99042 C -3.94581 -6.39717 -0.97854 H -4.10544 -6.8081 -1.98225 H -2.95777 -6.70947 -0.61984 H -4.71422 -6.77759 -0.3042 O -5.79749 -4.80904 0.49584 C -4.98164 -4.25803 -0.23059 C -5.59762 -1.79143 -0.03087 C -6.61472 -1.79556 1.03404 C -5.62043 -0.37151 -0.58451 C -7.05436 -2.73157 1.98142 C -7.17352 -0.49134 1.0886 N -6.59022 0.31903 0.11747 O -4.97763 0.12571 -1.50002 C -8.02754 -2.36842 2.91788 H -6.65356 -3.73282 1.97357 C -8.14411 -0.12035 2.00877 C -6.91996 1.70454 -0.13892 C -8.57285 -1.08376 2.92932 H -8.55338 0.88478 2.01853

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H -7.97408 1.8077 -0.42174 H -6.72762 2.32215 0.74646 H -6.28849 2.04275 -0.96152 H -9.33394 -0.8217 3.65937 H -8.36381 -3.10466 3.64196 C 0.5371 2.52407 -5.39209 C 1.90599 2.86969 -5.35676 C -0.36418 3.3983 -6.02491 C 2.36715 4.04025 -5.96296 H 2.6043 2.22055 -4.85538 C 0.05863 4.59513 -6.60698 H -1.41709 3.13295 -6.08075 C 1.41157 4.8991 -6.56572 C 3.67881 4.70508 -6.06402 H -0.65444 5.2629 -7.0796 N 2.03554 6.04505 -7.04792 C 3.39014 6.02696 -6.76354 C 4.9457 4.30639 -5.7036 C 1.38278 7.14134 -7.73071 O 4.15136 6.92756 -7.09016 C 6.23034 5.02444 -5.64389 C 5.28286 2.87312 -5.3082 H 0.89909 6.79275 -8.65058 H 0.62751 7.60854 -7.08736 H 2.1516 7.8741 -7.97943 C 6.62873 6.35865 -5.81103 C 7.21981 4.08684 -5.24659 N 6.64528 2.82941 -5.07748 O 4.56186 1.88675 -5.23367 C 7.96562 6.71575 -5.60815 H 5.907 7.10135 -6.11211 C 8.55064 4.42733 -5.04756 C 7.34726 1.62259 -4.69731 C 8.91764 5.76448 -5.23868 H 8.26225 7.7512 -5.74705 H 9.28169 3.6831 -4.74827 H 8.12079 1.37414 -5.43336 H 7.81721 1.7375 -3.71327 H 6.61254 0.81738 -4.6571 H 9.95348 6.05894 -5.09287

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Geometry coordinates for IIT-Br2’: C -0.53389 -1.24476 -3.6549 C 0.73206 -1.34251 -4.12703 C 1.34918 -0.23362 -4.82366 C 0.66831 0.92156 -5.01357 H 1.29918 -2.25923 -3.97985 H 2.36262 -0.3343 -5.20606 Te -1.2725 0.72563 -4.11104 C -1.37051 -2.24169 -3.00067 C -2.41578 -1.84842 -2.14225 C -1.14642 -3.61505 -3.22679 C -3.22196 -2.79723 -1.51476 H -2.59486 -0.80171 -1.95166 C -1.90711 -4.58713 -2.58056 H -0.37745 -3.92331 -3.92799 C -2.92451 -4.16784 -1.72965 C -4.33326 -2.73337 -0.55125 H -1.71672 -5.64154 -2.75207 N -3.77178 -4.96276 -0.97264 C -3.77094 -6.41034 -0.93391 H -3.9884 -6.82534 -1.92468 H -2.80135 -6.79117 -0.59215 H -4.54889 -6.71678 -0.23346 O -5.45538 -4.66043 0.55743 C -4.62453 -4.18274 -0.20133 C -5.0634 -1.67418 -0.06444 C -6.0587 -1.56987 1.01202 C -4.99719 -0.27495 -0.67175 C -6.54909 -2.44351 1.99385 C -6.51781 -0.22612 1.0325 N -5.89622 0.50771 0.02442 O -4.34447 0.13513 -1.62228 C -7.47526 -1.98072 2.93341 H -6.22329 -3.47174 2.01029 C -7.44 0.24352 1.95694 C -6.13081 1.90516 -0.27376 C -7.92142 -0.65814 2.91351 H -7.77327 1.27615 1.94317 H -7.17946 2.07321 -0.54496 H -5.87958 2.53426 0.58806

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H -5.49056 2.17131 -1.11561 H -8.64661 -0.31801 3.64783 H -7.85327 -2.66707 3.68524 C 1.11958 2.16126 -5.6345 C 2.48386 2.51202 -5.5472 C 0.23278 2.9958 -6.33893 C 2.96163 3.66131 -6.17698 H 3.15961 1.88605 -4.98793 C 0.67526 4.1696 -6.94731 H -0.80881 2.70562 -6.44859 C 2.02472 4.48758 -6.85306 C 4.2698 4.33587 -6.24337 H -0.01816 4.81109 -7.4808 N 2.65694 5.61963 -7.34613 C 4.00037 5.62774 -6.99879 C 5.52153 3.95978 -5.81379 C 2.02597 6.68619 -8.0957 O 4.76403 6.52617 -7.32183 C 6.79579 4.68906 -5.71822 C 5.8491 2.54151 -5.35646 H 1.58813 6.30099 -9.02356 H 1.23938 7.16774 -7.50297 H 2.79956 7.41703 -8.33467 C 7.19227 6.02006 -5.91504 C 7.7704 3.7741 -5.23962 N 7.19677 2.51784 -5.05494 O 5.13056 1.55255 -5.29098 C 8.51494 6.39536 -5.66035 H 6.48109 6.74525 -6.27777 C 9.0871 4.133 -4.98804 C 7.88784 1.33126 -4.59731 C 9.45352 5.46572 -5.20987 H 8.81154 7.42738 -5.82221 H 9.80785 3.40698 -4.62587 H 8.69682 1.06204 -5.28634 H 8.30932 1.48716 -3.59729 H 7.15741 0.52204 -4.56142 H 10.47877 5.77413 -5.02397 Br -2.25279 -0.20559 -6.49097 Br -0.20339 1.68321 -1.79298

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Geometry coordinates for IIT-Cl2’: C -0.51052 -1.23006 -3.60084 C 0.75817 -1.31709 -4.06673 C 1.37059 -0.20362 -4.76228 C 0.68326 0.94656 -4.95784 H 1.33227 -2.22904 -3.91756 H 2.38656 -0.29874 -5.13916 Te -1.25908 0.7339 -4.06457 C -1.34601 -2.23109 -2.95313 C -2.41669 -1.84409 -2.12353 C -1.09529 -3.60381 -3.15591 C -3.2191 -2.79686 -1.49745 H -2.62324 -0.7985 -1.95597 C -1.85517 -4.57898 -2.51427 H -0.30655 -3.90945 -3.83589 C -2.89667 -4.16518 -1.68986 C -4.34955 -2.73863 -0.55561 H -1.64577 -5.63237 -2.66877 N -3.74835 -4.96434 -0.94324 C -3.73062 -6.41155 -0.89219 H -3.91943 -6.83732 -1.88426 H -2.76488 -6.77734 -0.52422 H -4.52123 -6.72179 -0.20779 O -5.47362 -4.67131 0.54113 C -4.63045 -4.18883 -0.20069 C -5.09694 -1.68431 -0.08413 C -6.10991 -1.58556 0.97653 C -5.02999 -0.28466 -0.69072 C -6.6112 -2.46156 1.95082 C -6.57702 -0.24447 0.9894 N -5.9439 0.49282 -0.00895 O -4.36453 0.12963 -1.63074 C -7.55443 -2.00364 2.87561 H -6.28036 -3.488 1.97287 C -7.51626 0.22034 1.89899 C -6.18153 1.8891 -0.3105 C -8.00755 -0.68358 2.84832 H -7.85492 1.25112 1.87963 H -7.22694 2.05139 -0.59715 H -5.94642 2.51927 0.55505

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H -5.53039 2.15893 -1.14274 H -8.746 -0.34725 3.57107 H -7.94041 -2.69195 3.62158 C 1.12703 2.18943 -5.57569 C 2.49554 2.53113 -5.51499 C 0.23143 3.03742 -6.25237 C 2.96755 3.68165 -6.14559 H 3.17942 1.89719 -4.9751 C 0.6686 4.21314 -6.86072 H -0.81602 2.76058 -6.33826 C 2.02219 4.52037 -6.7945 C 4.27916 4.34702 -6.23535 H -0.03218 4.8646 -7.37194 N 2.65177 5.65146 -7.29193 C 4.00285 5.64682 -6.97417 C 5.53708 3.95793 -5.83658 C 2.01227 6.72966 -8.01746 O 4.7656 6.54242 -7.30662 C 6.819 4.67632 -5.76493 C 5.86366 2.5336 -5.39683 H 1.5507 6.35622 -8.93854 H 1.24313 7.21153 -7.40255 H 2.78589 7.45682 -8.26726 C 7.22151 6.00571 -5.96064 C 7.79699 3.75 -5.31603 N 7.21765 2.49684 -5.12763 O 5.13862 1.55008 -5.3208 C 8.5526 6.36858 -5.73354 H 6.50808 6.73941 -6.30112 C 9.12193 4.09652 -5.09205 C 7.90977 1.30136 -4.69521 C 9.49376 5.42806 -5.3119 H 8.8537 7.39949 -5.89412 H 9.84495 3.36202 -4.75225 H 8.70181 1.0329 -5.40387 H 8.35361 1.44536 -3.70312 H 7.17457 0.49692 -4.65079 H 10.52543 5.72697 -5.14721 Cl -0.2513 1.64858 -1.86646 Cl -2.16247 -0.1796 -6.31806

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Density Functional Theory Data for Chapter 3

Geometry coordinates for PT (B3LYP, 6-31g(d)/LANL2DZ) C -0.66544 -0.56861 -0.43047 C 0.53077 -0.3634 0.2042 C 1.00653 0.97247 0.38721 C 0.25591 2.02134 -0.07357 H 1.1255 -1.20724 0.54715 H 1.94608 1.15122 0.90548 C -1.3168 -1.85734 -0.68541 C -2.15281 -2.05781 -1.7997 C -1.11645 -2.94325 0.19077 C -2.75546 -3.29161 -2.03587 H -2.31061 -1.2427 -2.50231 C -1.71284 -4.17861 -0.05066 H -0.50664 -2.80382 1.07832 C -2.53616 -4.36063 -1.16454 H -3.39231 -3.41933 -2.90718 H -1.54463 -4.99894 0.64227 H -3.00608 -5.32288 -1.34793 C 0.59471 3.44596 0.00024 C -0.39752 4.44189 0.06703 C 1.94247 3.85923 0.00653 C -0.06065 5.79149 0.14628 H -1.44564 4.15163 0.08164 C 2.27836 5.2081 0.09432 H 2.72725 3.11407 -0.08211 C 1.27972 6.18263 0.16385 H -0.84813 6.53844 0.20088 H 3.32534 5.5001 0.09443 H 1.5434 7.23482 0.22508 Te -1.49987 1.28679 -0.9774

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Geometry coordinates for PT-Br2 (B3LYP, 6-31g(d)/LANL2DZ) C -0.60328 -0.61303 -0.4135 C 0.53249 -0.37644 0.28098 C 1.00704 0.98024 0.47935 C 0.31721 2.03018 -0.02106 H 1.10515 -1.20957 0.68275 H 1.91768 1.15196 1.04917 C -1.28101 -1.87967 -0.67882 C -1.92353 -2.12378 -1.90663 C -1.29067 -2.88892 0.3032 C -2.5438 -3.34677 -2.14949 H -1.89703 -1.36813 -2.68765 C -1.90932 -4.11158 0.05342 H -0.83487 -2.69582 1.26953 C -2.53853 -4.34481 -1.17187 H -3.02729 -3.52211 -3.1063 H -1.91443 -4.87753 0.8239 H -3.02801 -5.29599 -1.36112 C 0.64027 3.45406 0.01599 C -0.36382 4.43062 0.15031 C 1.98239 3.87137 -0.07303 C -0.03359 5.78229 0.20884 H -1.40189 4.12502 0.2542 C 2.30738 5.22414 -0.0093 H 2.76231 3.13043 -0.21953 C 1.30207 6.18409 0.13048 H -0.82092 6.52217 0.32121 H 3.347 5.53021 -0.08599 H 1.55747 7.23922 0.17072 Te -1.41569 1.27487 -1.04727 Br -2.83179 1.40372 1.28121 Br 0.04898 1.12191 -3.34426

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Geometry coordinates for PT-Cl2 (B3LYP, 6-31g(d)/LANL2DZ) C -0.60291 -0.61528 -0.41286 C 0.52919 -0.37656 0.28609 C 1.00395 0.98142 0.48461 C 0.31858 2.03145 -0.02021 H 1.09999 -1.20813 0.6935 H 1.91195 1.15241 1.05874 C -1.28261 -1.87997 -0.67765 C -1.95082 -2.11343 -1.89375 C -1.26785 -2.90044 0.29313 C -2.5712 -3.33614 -2.1375 H -1.94809 -1.34918 -2.66688 C -1.88668 -4.12251 0.04279 H -0.79302 -2.71667 1.25202 C -2.54079 -4.3449 -1.17161 H -3.07509 -3.50232 -3.08528 H -1.87267 -4.89681 0.80471 H -3.03071 -5.29581 -1.36082 C 0.64097 3.45494 0.01422 C -0.36476 4.43209 0.13095 C 1.98438 3.87177 -0.05848 C -0.03532 5.78387 0.1903 H -1.40492 4.12836 0.21841 C 2.30845 5.2246 0.005 H 2.76614 3.1305 -0.19276 C 1.30139 6.18503 0.1288 H -0.82396 6.52416 0.28949 H 3.34892 5.53045 -0.05962 H 1.55638 7.24022 0.16901 Te -1.40594 1.2727 -1.05675 Cl 0.01609 1.12276 -3.21148 Cl -2.76106 1.39375 1.14329

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Geometry coordinates for PT-F2 (B3LYP, 6-31g(d)/LANL2DZ) C -0.67283 -0.58796 -0.31969 C 0.49657 -0.37297 0.31905 C 1.01968 0.98538 0.44395 C 0.35843 2.01622 -0.12328 H 1.06867 -1.20825 0.71932 H 1.92717 1.16121 1.01907 C -1.31808 -1.8674 -0.61541 C -1.83259 -2.11463 -1.90171 C -1.42346 -2.87148 0.36294 C -2.42861 -3.33709 -2.2012 H -1.71165 -1.35676 -2.67153 C -2.02108 -4.09363 0.05782 H -1.05533 -2.67745 1.36629 C -2.52715 -4.33001 -1.22244 H -2.8112 -3.51755 -3.20205 H -2.10244 -4.85838 0.82558 H -2.99865 -5.28075 -1.45537 C 0.67387 3.44278 -0.04472 C -0.34429 4.37458 0.23007 C 1.98868 3.90675 -0.22499 C -0.05134 5.73246 0.32896 H -1.35267 4.01308 0.41468 C 2.27655 5.26725 -0.12478 H 2.77503 3.19708 -0.46567 C 1.2591 6.18412 0.14954 H -0.84622 6.43877 0.55241 H 3.29596 5.6131 -0.27343 H 1.4851 7.24452 0.2197 Te -1.41139 1.27376 -1.0484 F -0.34004 0.84805 -2.64076 F -2.22403 1.58463 0.71391

  14

Geometry coordinates for PT (B3LYP, 6-31g(d)/SDD) C -0.66456 -0.56668 -0.4312 C 0.53213 -0.36387 0.20338 C 1.00825 0.97217 0.38568 C 0.25555 2.01947 -0.07538 H 1.12531 -1.20917 0.54537 H 1.94769 1.15327 0.90331 C -1.31703 -1.85542 -0.68673 C -2.13275 -2.06337 -1.81464 C -1.13568 -2.93309 0.20334 C -2.73468 -3.29787 -2.04983 H -2.27394 -1.25464 -2.52806 C -1.73179 -4.16892 -0.03701 H -0.54107 -2.78639 1.10003 C -2.53512 -4.35886 -1.16401 H -3.35545 -3.43242 -2.93164 H -1.5791 -4.98311 0.66666 H -3.00492 -5.3213 -1.34669 C 0.59288 3.445 -0.00096 C -0.39927 4.43901 0.09107 C 1.94016 3.85896 -0.01777 C -0.06168 5.78845 0.17241 H -1.44652 4.14721 0.12491 C 2.27658 5.20768 0.07173 H 2.72327 3.11451 -0.12558 C 1.27852 6.1806 0.16637 H -0.84844 6.53439 0.24732 H 3.32308 5.5008 0.05347 H 1.54241 7.23265 0.22896 Te -1.49585 1.28496 -0.97599

  15

Geometry coordinates for PT-Br2 (B3LYP, 6-31g(d)/SDD) C -0.6009 -0.61375 -0.40815 C 0.53614 -0.37837 0.28588 C 1.01102 0.97796 0.48371 C 0.32114 2.02761 -0.01888 H 1.10861 -1.21155 0.68751 H 1.92151 1.1497 1.05352 C -1.28129 -1.87855 -0.67468 C -1.95846 -2.10667 -1.88701 C -1.25782 -2.9042 0.29041 C -2.57891 -3.32909 -2.13239 H -1.96049 -1.33845 -2.6561 C -1.87705 -4.12587 0.03838 H -0.7752 -2.72522 1.24637 C -2.53994 -4.34295 -1.17213 H -3.0892 -3.49097 -3.07753 H -1.85614 -4.90416 0.79609 H -3.02964 -5.2937 -1.36281 C 0.64244 3.45189 0.01477 C -0.36453 4.43052 0.10772 C 1.98702 3.86882 -0.03555 C -0.03588 5.78266 0.16493 H -1.4061 4.12763 0.1794 C 2.31031 5.22188 0.02626 H 2.77156 3.12719 -0.15049 C 1.30168 6.18347 0.12578 H -0.82633 6.52334 0.24514 H 3.35198 5.52695 -0.02056 H 1.55623 7.23881 0.16469 Te -1.40935 1.27196 -1.04136 Br -2.84554 1.40115 1.27594 Br 0.04109 1.13431 -3.34943

  16

Geometry coordinates for PT (CAM-B3LYP, 6-31g(d)/SDD) C -0.66427 -0.55337 -0.43509 C 0.52352 -0.36164 0.19715 C 1.00054 0.9778 0.37988 C 0.24783 2.01027 -0.08369 H 1.11119 -1.20853 0.54109 H 1.93804 1.16361 0.897 C -1.31427 -1.84616 -0.68945 C -2.066 -2.07416 -1.84775 C -1.18883 -2.89175 0.2344 C -2.66335 -3.30588 -2.08067 H -2.16281 -1.28303 -2.58643 C -1.78042 -4.12525 -0.00191 H -0.63842 -2.72254 1.15408 C -2.52119 -4.33841 -1.15992 H -3.23736 -3.46056 -2.9891 H -1.67211 -4.92066 0.72916 H -2.98865 -5.30112 -1.34109 C 0.5877 3.43731 -0.00433 C -0.3967 4.4182 0.16169 C 1.92384 3.84947 -0.09074 C -0.05882 5.76225 0.24904 H -1.43845 4.121 0.24757 C 2.2621 5.19255 0.00372 H 2.6979 3.10687 -0.25432 C 1.27285 6.15579 0.17331 H -0.84 6.50417 0.38302 H 3.3041 5.4892 -0.06809 H 1.53768 7.20624 0.24082 Te -1.48764 1.28236 -0.98083

  17

Geometry coordinates for PT-Br2 (CAM-B3LYP, 6-31g(d)/SDD) C -0.60068 -0.5998 -0.40828 C 0.52876 -0.3782 0.2823 C 1.00636 0.98336 0.47956 C 0.31329 2.01709 -0.02335 H 1.0942 -1.21422 0.68441 H 1.91703 1.16121 1.0447 C -1.27922 -1.86885 -0.67851 C -1.8533 -2.13088 -1.92751 C -1.35149 -2.84481 0.32158 C -2.47251 -3.34833 -2.17323 H -1.77752 -1.39283 -2.72122 C -1.96909 -4.0626 0.06999 H -0.94196 -2.6321 1.30352 C -2.53148 -4.31731 -1.1763 H -2.90561 -3.54229 -3.14918 H -2.02364 -4.80927 0.85576 H -3.02034 -5.26696 -1.36896 C 0.63446 3.4449 0.0148 C -0.3616 4.40573 0.22174 C 1.95965 3.86371 -0.14828 C -0.03557 5.75351 0.27846 H -1.38954 4.0914 0.38001 C 2.28163 5.21279 -0.08686 H 2.73048 3.1266 -0.34733 C 1.28612 6.16065 0.1254 H -0.8167 6.48745 0.4482 H 3.31243 5.52523 -0.22013 H 1.53863 7.21544 0.16541 Te -1.3964 1.2665 -1.03412 Br -2.77721 1.38507 1.27054 Br 0.06877 1.11013 -3.28368

  18

Density Functional Theory Data for Chapter 4 Geometry Coordinates for PT-R Structures PT (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.63449 -0.62927 -0.41841 C 0.5697 -0.36422 0.17086 C 0.99077 0.99352 0.31998 C 0.17738 1.998 -0.12403 H 1.21054 -1.17609 0.50445 H 1.9382 1.22317 0.8003 C -1.24116 -1.949 -0.62423 C -2.00509 -2.24099 -1.76658 C -1.0655 -2.96893 0.32826 C -2.56452 -3.50121 -1.9539 H -2.14016 -1.47949 -2.5289 C -1.6185 -4.23107 0.13595 H -0.51107 -2.75849 1.23647 C -2.37234 -4.50441 -1.00494 H -3.14626 -3.70189 -2.84801 H -1.47184 -5.00016 0.8879 H -2.80883 -5.48706 -1.15075 C 0.45613 3.43757 -0.08268 C -0.56141 4.38128 0.13626 C 1.76823 3.91348 -0.2569 C -0.27979 5.74297 0.18765 H -1.58081 4.04214 0.29444 C 2.0499 5.27465 -0.19725 H 2.56627 3.20869 -0.46395 C 1.02799 6.19747 0.02392 H -1.084 6.45033 0.36376 H 3.07031 5.61698 -0.33858 H 1.24778 7.25931 0.06348 Te -1.56471 1.17386 -0.95529 SCF Done: E(RB3LYP) = -625.092135084

  19

PT-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.60868 -0.60856 -0.42458 C 0.52143 -0.37025 0.27008 C 0.99242 0.98505 0.47333 C 0.30553 2.03331 -0.02279 H 1.09457 -1.20147 0.67181 H 1.90142 1.15493 1.04399 C -1.29069 -1.87334 -0.67807 C -1.94335 -2.12333 -1.89604 C -1.28212 -2.88263 0.30067 C -2.54677 -3.3525 -2.13708 H -1.93905 -1.37051 -2.67807 C -1.88725 -4.11015 0.05537 H -0.82466 -2.68797 1.26432 C -2.52207 -4.35001 -1.16304 H -3.0353 -3.53203 -3.08895 H -1.879 -4.87508 0.82489 H -2.99957 -5.3061 -1.34999 C 0.63597 3.45399 0.00526 C -0.35958 4.43637 0.13047 C 1.97906 3.86331 -0.0683 C -0.02166 5.783 0.20485 H -1.4015 4.14464 0.21825 C 2.31245 5.21094 0.0065 H 2.75679 3.12191 -0.21376 C 1.31471 6.17584 0.14275 H -0.80418 6.52645 0.31375 H 3.35336 5.50996 -0.06029 H 1.5767 7.22741 0.19387 Te -1.42105 1.27795 -1.05377 Br -2.88603 1.37316 1.29888 Br 0.07607 1.16804 -3.38485 SCF Done: E(RB3LYP) = -5773.39794694

  20

PT-tBu (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.68679 -0.55395 -0.46656 C 0.48735 -0.34578 0.20117 C 0.95922 0.99073 0.38697 C 0.22411 2.03399 -0.1022 H 1.06706 -1.1875 0.57088 H 1.88262 1.17397 0.93007 C -1.33898 -1.84245 -0.71841 C -2.04713 -2.10378 -1.89838 C -1.26932 -2.88026 0.22806 C -2.64783 -3.33987 -2.12775 H -2.10989 -1.33872 -2.66698 C -1.86571 -4.11084 -0.00975 H -0.7615 -2.7078 1.17119 C -2.57235 -4.37838 -1.19321 H -3.17597 -3.48352 -3.06239 H -1.78621 -4.87414 0.75744 C 0.5625 3.45827 -0.03135 C -0.41491 4.45225 0.10498 C 1.90165 3.88439 -0.08811 C -0.07563 5.8007 0.19172 H -1.46167 4.16991 0.17308 C 2.23247 5.22921 0.00449 H 2.68926 3.15197 -0.23044 C 1.25586 6.22783 0.14793 H -0.87751 6.51995 0.30434 H 3.28133 5.5023 -0.04973 Te -1.49678 1.29272 -1.04971 C -3.21895 -5.75586 -1.41364 C 1.6687 7.70549 0.24711 C -2.1238 -6.84682 -1.39395 H -1.58432 -6.86881 -0.44403 H -2.56605 -7.83674 -1.54498 H -1.38922 -6.68171 -2.1871 C -4.2388 -6.03617 -0.28629 H -5.03081 -5.28219 -0.27574 H -4.70722 -7.01507 -0.4293 H -3.77012 -6.03712 0.70055

  21

C -3.95942 -5.84658 -2.75951 H -4.77291 -5.11912 -2.83098 H -3.28871 -5.69153 -3.60918 H -4.40133 -6.84045 -2.87198 C 2.44089 8.11453 -1.02797 H 2.74624 9.1641 -0.97004 H 3.34405 7.51626 -1.16968 H 1.8201 7.99316 -1.92002 C 0.45669 8.64254 0.39362 H -0.11994 8.43002 1.29824 H 0.79659 9.67966 0.46157 H -0.21969 8.57813 -0.46344 C 2.57941 7.90279 1.48052 H 2.05993 7.62437 2.40165 H 3.48858 7.29988 1.41887 H 2.88397 8.95056 1.56848 SCF Done: E(RB3LYP) = -939.664884226

  22

PT-tBu-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.58318 -0.6069 -0.53707 C 0.66438 -0.37322 -0.08264 C 1.13746 0.98126 0.11895 C 0.3375 2.03604 -0.13802 H 1.32844 -1.20833 0.12365 H 2.14414 1.14508 0.49379 C -1.27832 -1.87263 -0.73199 C -2.16865 -2.07411 -1.79896 C -1.05529 -2.94535 0.14251 C -2.78528 -3.30185 -1.98785 H -2.34729 -1.27786 -2.51532 C -1.67705 -4.17422 -0.05856 H -0.41073 -2.80844 1.00405 C -2.55774 -4.38691 -1.12555 H -3.45517 -3.41274 -2.83358 H -1.4756 -4.96719 0.65082 C 0.63153 3.46127 -0.07176 C -0.33366 4.40223 0.30719 C 1.92325 3.93394 -0.36458 C -0.01769 5.75364 0.41258 H -1.33615 4.0779 0.56971 C 2.22832 5.28178 -0.25271 H 2.68274 3.23995 -0.70797 C 1.26921 6.23059 0.13915 H -0.80026 6.43527 0.72048 H 3.23646 5.59944 -0.4963 Te -1.55214 1.28817 -0.83301 Br -2.48764 1.16617 1.776 Br -0.58906 1.41013 -3.43285 C 1.6503 7.71594 0.2402 C -3.26427 -5.72863 -1.37486 C -2.90205 -6.78666 -0.31821 H -3.1944 -6.4786 0.68948 H -3.42645 -7.72074 -0.5368 H -1.83162 -7.01042 -0.30968 C -2.85214 -6.27105 -2.76275 H -3.12251 -5.58442 -3.56828

  23

H -1.77248 -6.43617 -2.81676 H -3.34891 -7.22564 -2.96209 C -4.79556 -5.51802 -1.3406 H -5.31383 -6.46621 -1.51311 H -5.11845 -5.12953 -0.37083 H -5.13145 -4.81567 -2.10693 C 2.78661 7.88309 1.27525 H 3.6821 7.32316 0.99563 H 3.07032 8.93638 1.3622 H 2.47347 7.53627 2.26387 C 0.46719 8.59565 0.68054 H -0.3656 8.54952 -0.02665 H 0.09117 8.31574 1.66851 H 0.78573 9.63986 0.73841 C 2.13654 8.21598 -1.1396 H 1.35449 8.10865 -1.89619 H 2.41079 9.27407 -1.0863 H 3.01328 7.66622 -1.48936 SCF Done: E(RB3LYP) = -6087.97227378

  24

PT-OtBu (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.46068 -0.63193 -0.44745 C 0.69307 -0.42751 0.25568 C 1.09731 0.90813 0.56962 C 0.32329 1.9574 0.1607 H 1.30881 -1.27078 0.55821 H 2.00382 1.08446 1.14312 C -1.05155 -1.91914 -0.8214 C -1.72973 -2.10546 -2.03998 C -0.95504 -3.0318 0.02521 C -2.26672 -3.33228 -2.39016 H -1.81439 -1.27845 -2.73877 C -1.4868 -4.27388 -0.31796 H -0.4731 -2.92336 0.99122 C -2.15284 -4.44158 -1.53754 H -2.77991 -3.46349 -3.33641 H -1.38511 -5.08557 0.3866 C 0.59936 3.38417 0.34443 C -0.42427 4.32263 0.57017 C 1.91114 3.87618 0.309 C -0.14772 5.66622 0.75554 H -1.45602 3.98815 0.62638 C 2.20356 5.22565 0.50068 H 2.72875 3.19382 0.10152 C 1.17201 6.14393 0.7272 H -0.94652 6.37721 0.93555 H 3.23618 5.53679 0.45115 Te -1.34877 1.22323 -0.88001 O -2.74258 -5.57509 -2.0146 O 1.28214 7.48972 0.91869 C -2.68725 -6.90269 -1.41222 C 2.51943 8.25882 0.99335 C -1.24104 -7.39767 -1.29178 H -0.65485 -6.84032 -0.56176 H -1.23513 -8.44786 -0.98774 H -0.73484 -7.32323 -2.25714 C -3.44442 -6.93622 -0.078 H -4.44823 -6.52403 -0.20436

  25

H -3.54513 -7.97003 0.26366 H -2.94873 -6.37627 0.71459 C -3.43605 -7.75458 -2.44218 H -2.93223 -7.71675 -3.4103 H -3.48477 -8.79691 -2.11751 H -4.45545 -7.38599 -2.57508 C 2.00178 9.6755 1.26253 H 2.83328 10.3799 1.34396 H 1.34772 10.00481 0.45234 H 1.43109 9.70458 2.19312 C 3.38836 7.80008 2.17083 H 2.80731 7.81111 3.09594 H 3.7947 6.79742 2.04148 H 4.23179 8.48486 2.29398 C 3.2672 8.23669 -0.34634 H 3.69256 7.26315 -0.58863 H 2.59363 8.52119 -1.15806 H 4.08876 8.95778 -0.32192 SCF Done: E(RB3LYP) = -1090.13712630

  26

PT-OtBu-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.33179 -0.69425 -0.5144 C 0.80977 -0.45304 0.16273 C 1.19208 0.89747 0.51923 C 0.41539 1.94863 0.18403 H 1.45735 -1.28186 0.43656 H 2.11172 1.06315 1.0742 C -0.95037 -1.95946 -0.87735 C -1.61656 -2.13961 -2.10415 C -0.88039 -3.05909 -0.01098 C -2.15871 -3.36278 -2.44869 H -1.67237 -1.32201 -2.81627 C -1.42098 -4.29586 -0.35 H -0.41682 -2.94011 0.96233 C -2.07326 -4.46446 -1.57888 H -2.66022 -3.49912 -3.4 H -1.34407 -5.10086 0.36466 C 0.65148 3.37312 0.35442 C -0.39084 4.27392 0.64283 C 1.94942 3.89516 0.26165 C -0.13807 5.61619 0.85123 H -1.40838 3.9108 0.75012 C 2.21469 5.2446 0.47237 H 2.76929 3.23807 -0.00746 C 1.16886 6.12826 0.77135 H -0.94386 6.3025 1.08517 H 3.23312 5.588 0.37508 O -2.66138 -5.59085 -2.05502 O 1.25428 7.46411 0.99283 C -2.74009 -6.89051 -1.387 C 2.472 8.2755 1.00674 C -1.34281 -7.48503 -1.17643 H -0.74818 -6.94088 -0.44322 H -1.43165 -8.51712 -0.82674 H -0.79031 -7.49541 -2.11877 C -3.55518 -6.79558 -0.09203 H -4.51781 -6.31701 -0.28557 H -3.74977 -7.8001 0.29322

  27

H -3.0533 -6.23479 0.69594 C -3.5054 -7.7305 -2.41366 H -2.95885 -7.77436 -3.35799 H -3.64513 -8.75028 -2.0471 H -4.48787 -7.29581 -2.60904 C 1.92409 9.66604 1.34135 H 2.73449 10.3978 1.38198 H 1.20628 9.98744 0.58388 H 1.41736 9.65694 2.30857 C 3.42575 7.81885 2.11665 H 2.8991 7.77288 3.07267 H 3.87091 6.84183 1.93003 H 4.24273 8.53836 2.21678 C 3.1297 8.30426 -0.37808 H 3.56461 7.34923 -0.67178 H 2.39849 8.58911 -1.13801 H 3.93188 9.04698 -0.38764 Te -1.30048 1.1937 -0.87088 Br -2.67238 0.88646 1.52366 Br 0.08707 1.4994 -3.25642 SCF Done: E(RB3LYP) = -6238.44661746

  28

PT-NEt2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.496 -0.63919 -0.39359 C 0.69389 -0.42971 0.24673 C 1.15752 0.90677 0.45278 C 0.40537 1.95767 0.00572 H 1.29304 -1.27246 0.58225 H 2.09329 1.08362 0.97698 C -1.14908 -1.92304 -0.64804 C -1.93126 -2.15946 -1.78719 C -1.00982 -2.99915 0.24717 C -2.53321 -3.38772 -2.0326 H -2.04397 -1.37463 -2.53007 C -1.60668 -4.22783 0.01588 H -0.44938 -2.85699 1.16537 C -2.39273 -4.46487 -1.13374 H -3.0856 -3.50582 -2.95558 H -1.49408 -5.00284 0.764 C 0.73664 3.3799 0.08553 C -0.24153 4.37621 0.21108 C 2.0728 3.8194 0.05233 C 0.07957 5.72489 0.30685 H -1.28822 4.0923 0.27733 C 2.40638 5.16083 0.1451 H 2.86816 3.09438 -0.08592 C 1.41892 6.16261 0.27366 H -0.72946 6.42976 0.44634 H 3.45141 5.4369 0.07375 Te -1.3352 1.21735 -0.91439 N -3.00072 -5.70762 -1.3331 N 1.78191 7.51131 0.34516 C -3.91373 -5.89159 -2.4595 H -3.35651 -6.10499 -3.38806 H -4.44113 -4.95122 -2.6186 C -2.31222 -6.90954 -0.84565 H -2.33663 -7.66364 -1.6404 H -1.25474 -6.67206 -0.70106 C 0.73926 8.53545 0.33865 H 0.31356 8.67124 1.348

  29

H -0.0708 8.18208 -0.2993 C 3.03584 7.86055 1.0261 H 3.33228 7.0232 1.66364 H 2.8329 8.69199 1.71096 C -4.96651 -6.97731 -2.2355 H -5.63521 -7.01473 -3.10015 H -4.53327 -7.97314 -2.12079 H -5.56983 -6.76281 -1.35002 C -2.88859 -7.50618 0.44212 H -2.87114 -6.78257 1.26032 H -3.92408 -7.82568 0.3101 H -2.30295 -8.37882 0.74995 C 1.19896 9.8876 -0.20669 H 0.35007 10.57705 -0.22329 H 1.97704 10.35071 0.40379 H 1.5768 9.79157 -1.22752 C 4.19339 8.23652 0.09625 H 4.43522 7.42209 -0.59053 H 3.95613 9.11446 -0.50763 H 5.09078 8.46205 0.68197 SCF Done: E(RB3LYP) = -1050.37287656

  30

PT-NEt2-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.42153 -0.69906 -0.3605 C 0.72998 -0.45832 0.30637 C 1.18038 0.8925 0.54993 C 0.46248 1.9542 0.11937 H 1.33362 -1.29149 0.6565 H 2.1046 1.05459 1.09834 C -1.10588 -1.94929 -0.62378 C -1.91022 -2.14473 -1.75686 C -0.96169 -3.04632 0.24681 C -2.52139 -3.35921 -2.02484 H -2.02141 -1.34644 -2.4848 C -1.56438 -4.26312 -0.01053 H -0.39363 -2.92813 1.1633 C -2.36916 -4.46501 -1.15832 H -3.08802 -3.44726 -2.94171 H -1.44888 -5.05558 0.71731 C 0.76783 3.37045 0.16185 C -0.22984 4.35305 0.2532 C 2.10094 3.8223 0.14206 C 0.07235 5.70264 0.33742 H -1.27335 4.05906 0.31778 C 2.415 5.16594 0.22612 H 2.90545 3.10501 0.01938 C 1.40976 6.15869 0.32438 H -0.74877 6.39637 0.45413 H 3.45698 5.45184 0.16424 N -2.97708 -5.69218 -1.38837 N 1.74698 7.50431 0.38836 C -3.89539 -5.85926 -2.51623 H -3.33796 -6.09093 -3.43867 H -4.39875 -4.90786 -2.6823 C -2.34493 -6.90993 -0.86493 H -2.39287 -7.67608 -1.64549 H -1.27997 -6.71315 -0.71522 C 0.69981 8.52734 0.38226 H 0.31949 8.69777 1.40279 H -0.13478 8.14963 -0.20658

  31

C 3.04186 7.88967 0.9638 H 3.3802 7.09054 1.62886 H 2.87686 8.75706 1.61113 C -4.97634 -6.91607 -2.28968 H -5.64112 -6.93939 -3.15754 H -4.57082 -7.92256 -2.1686 H -5.57919 -6.68079 -1.40933 C -2.96011 -7.45642 0.42719 H -2.93253 -6.71636 1.23001 H -4.00259 -7.74716 0.28587 H -2.40656 -8.33936 0.76259 C 1.12972 9.85816 -0.23496 H 0.27663 10.54224 -0.23942 H 1.93138 10.34872 0.32101 H 1.46018 9.72489 -1.2678 C 4.13502 8.21602 -0.05825 H 4.33344 7.37044 -0.72054 H 3.85822 9.06513 -0.68576 H 5.06797 8.46721 0.45661 Te -1.28184 1.20047 -0.88867 Br -2.70929 1.19456 1.49732 Br 0.12665 1.22074 -3.28445 SCF Done: E(RB3LYP) = -6198.68463387

  32

PT-CN (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.64571 -0.62174 -0.41731 C 0.56186 -0.36017 0.17134 C 0.98562 0.99409 0.31298 C 0.16928 1.99755 -0.13425 H 1.20268 -1.17149 0.50499 H 1.93324 1.22289 0.79243 C -1.24676 -1.94104 -0.62212 C -2.04165 -2.22526 -1.74653 C -1.03581 -2.97264 0.31236 C -2.59715 -3.48113 -1.93849 H -2.20528 -1.45869 -2.49716 C -1.58063 -4.23369 0.1258 H -0.45815 -2.77289 1.20757 C -2.36936 -4.50117 -1.00325 H -3.20167 -3.68141 -2.8156 H -1.4111 -5.01399 0.85896 C 0.45108 3.43353 -0.08989 C -0.57022 4.38265 0.09235 C 1.77083 3.90503 -0.22411 C -0.29258 5.74003 0.14737 H -1.59568 4.05141 0.22087 C 2.05978 5.25948 -0.16291 H 2.57454 3.20012 -0.403 C 1.0289 6.19292 0.02295 H -1.09397 6.45468 0.29538 H 3.08182 5.60372 -0.27273 Te -1.57482 1.17757 -0.95958 C -2.939 -5.79788 -1.19544 C 1.32181 7.59069 0.07987 N -3.3991 -6.84685 -1.35092 N 1.55884 8.72112 0.12659 SCF Done: E(RB3LYP) = -809.629003433

  33

PT-CN-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.62513 -0.59798 -0.42695 C 0.50754 -0.36436 0.26563 C 0.98382 0.98982 0.4598 C 0.29466 2.03517 -0.04008 H 1.07988 -1.1956 0.66808 H 1.89368 1.15997 1.02875 C -1.29986 -1.8665 -0.68116 C -1.92974 -2.1292 -1.90881 C -1.31125 -2.86369 0.3101 C -2.52971 -3.35522 -2.15177 H -1.91063 -1.38718 -2.70017 C -1.90618 -4.09331 0.07258 H -0.87283 -2.66028 1.28012 C -2.5218 -4.34849 -1.16166 H -3.00035 -3.55142 -3.10789 H -1.91446 -4.85333 0.84507 C 0.62788 3.45495 -0.00399 C -0.36397 4.43792 0.14751 C 1.97041 3.86167 -0.10186 C -0.0287 5.78094 0.22507 H -1.40455 4.14956 0.25386 C 2.31333 5.20247 -0.02081 H 2.74465 3.12179 -0.2679 C 1.31491 6.17406 0.14257 H -0.80198 6.52873 0.35537 H 3.35052 5.50586 -0.10244 Te -1.4362 1.28448 -1.06328 Br -2.87297 1.38819 1.29957 Br 0.06768 1.15024 -3.38191 C 1.66582 7.55823 0.22045 C -3.14126 -5.61389 -1.40714 N 1.95123 8.67602 0.28531 N -3.63955 -6.6375 -1.60472 SCF Done: E(RB3LYP) = -5957.92918586

  34

PT-CF3 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.65442 -0.56349 -0.44349 C 0.53922 -0.36353 0.19342 C 1.01216 0.9705 0.37881 C 0.25497 2.01425 -0.07717 H 1.13287 -1.2075 0.53373 H 1.95003 1.15145 0.89664 C -1.30247 -1.85304 -0.70006 C -2.03749 -2.08975 -1.87329 C -1.19571 -2.90121 0.23203 C -2.63737 -3.31974 -2.11177 H -2.11707 -1.3104 -2.62436 C -1.78726 -4.13455 -0.00503 H -0.66234 -2.73703 1.16134 C -2.51057 -4.34976 -1.17973 H -3.19035 -3.48169 -3.02936 H -1.69152 -4.92798 0.7273 C 0.59006 3.43857 0.00642 C -0.39695 4.42035 0.19253 C 1.92801 3.86251 -0.0907 C -0.06693 5.76653 0.28404 H -1.4362 4.12544 0.29676 C 2.26381 5.20587 0.00754 H 2.70888 3.13187 -0.26792 C 1.2669 6.16497 0.19671 H -0.84576 6.50357 0.43932 H 3.3019 5.50846 -0.06965 Te -1.48944 1.2825 -0.98124 C -3.19841 -5.66648 -1.40513 C 1.62797 7.62271 0.243 F -3.40049 -5.92273 -2.71703 F -4.42003 -5.70861 -0.81131 F -2.49318 -6.70467 -0.89928 F 1.7198 8.16202 -1.00111 F 0.71258 8.35784 0.91334 F 2.82408 7.83457 0.83893 SCF Done: E(RB3LYP) = -1299.39458767

  35

PT-CF3 triplet state optimization (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 3 C -0.68711 -0.5693 -0.45672 C 0.57682 -0.34198 0.21548 C 1.03673 0.92488 0.37259 C 0.2598 2.03922 -0.1329 H 1.15163 -1.1796 0.5934 H 1.981 1.10163 0.87458 C -1.30192 -1.81834 -0.68899 C -2.55993 -1.92655 -1.35594 C -0.69584 -3.04538 -0.26819 C -3.16181 -3.14747 -1.58242 H -3.06849 -1.03186 -1.69935 C -1.3008 -4.26281 -0.49825 H 0.25931 -3.03188 0.24027 C -2.53883 -4.3304 -1.15949 H -4.11616 -3.18717 -2.09341 H -0.81068 -5.17189 -0.16856 C 0.5929 3.40722 -0.03599 C -0.24905 4.4276 -0.5737 C 1.7924 3.84543 0.61124 C 0.07398 5.76533 -0.47524 H -1.17283 4.15729 -1.07439 C 2.10976 5.1838 0.70833 H 2.47149 3.1216 1.04242 C 1.25502 6.16026 0.17017 H -0.59309 6.50925 -0.89391 H 3.02382 5.47984 1.21026 Te -1.51 1.30024 -1.05644 C -3.20506 -5.65597 -1.35143 C 1.64088 7.60407 0.2371 F -4.14955 -5.63222 -2.31931 F -3.83218 -6.08875 -0.21915 F -2.32489 -6.63415 -1.68227 F 2.51508 7.95372 -0.75114 F 0.58064 8.43515 0.11209 F 2.25625 7.92102 1.40347 SCF Done: E(UB3LYP) = -1299.33350264

  36

PT-CF3-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.62327 -0.59885 -0.42526 C 0.50372 -0.36518 0.27569 C 0.97855 0.98957 0.47398 C 0.29399 2.03468 -0.03126 H 1.07277 -1.19635 0.68298 H 1.88416 1.15977 1.0497 C -1.29705 -1.86736 -0.68646 C -1.92869 -2.12409 -1.91251 C -1.3019 -2.87215 0.29673 C -2.52552 -3.35379 -2.16102 H -1.91317 -1.37815 -2.70027 C -1.89335 -4.10257 0.0483 H -0.85991 -2.67597 1.26666 C -2.50681 -4.34639 -1.18215 H -2.99364 -3.54179 -3.11942 H -1.88921 -4.8676 0.81609 C 0.62575 3.45572 0.00629 C -0.36661 4.43728 0.15038 C 1.96792 3.86367 -0.07993 C -0.02968 5.78222 0.2307 H -1.40771 4.14884 0.25123 C 2.30671 5.20708 0.00438 H 2.745 3.12471 -0.23682 C 1.3081 6.1699 0.16012 H -0.80666 6.52567 0.36037 H 3.34619 5.5061 -0.0633 Te -1.4284 1.28362 -1.0679 Br -2.88699 1.39055 1.28282 Br 0.09259 1.14792 -3.37672 C -3.19205 -5.66582 -1.41929 C 1.67564 7.62955 0.19147 F 2.85987 7.84097 0.80843 F 0.7506 8.37548 0.83264 F 1.79338 8.14276 -1.0587 F -4.42255 -5.69997 -0.84988 F -3.3622 -5.92698 -2.73243 F -2.49513 -6.69814 -0.89144 SCF Done: E(RB3LYP) = -6447.69613630

  37

PT-C6F5 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.62869 -0.63937 -0.3912 C 0.59166 -0.36781 0.18486 C 1.02237 0.97846 0.3087 C 0.20905 1.99502 -0.13886 H 1.23909 -1.15372 0.5459 H 1.98508 1.17445 0.75796 C -1.22901 -1.96175 -0.57999 C -2.43473 -2.14658 -1.28058 C -0.66949 -3.15826 -0.08507 C -3.034 -3.37899 -1.4871 C -1.24803 -4.40493 -0.27701 C -2.43757 -4.52591 -0.98303 C 0.50223 3.42923 -0.09714 C -0.43042 4.39889 -0.50801 C 1.72531 3.97083 0.35082 C -0.19714 5.76468 -0.48081 C 1.98545 5.33338 0.38889 C 1.02321 6.24405 -0.02682 Te -1.5469 1.16748 -0.9434 F 0.47445 -3.14648 0.61724 F -0.66053 -5.49602 0.2213 F -2.99651 -5.72077 -1.17076 F -4.17967 -3.46409 -2.16765 F -3.0778 -1.07726 -1.79463 F 2.72175 3.17406 0.76828 F -1.63881 4.0096 -0.96577 F -1.14103 6.61652 -0.88872 F 1.26834 7.55324 0.00796 F 3.16832 5.77402 0.82544 SCF Done: E(RB3LYP) = -1617.71506298

  38

PT-C6F5-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.63803 -0.66526 -0.33787 C 0.5687 -0.37303 0.20313 C 1.01983 0.9943 0.301 C 0.25031 2.01031 -0.15736 H 1.22097 -1.15145 0.57424 H 1.98651 1.17989 0.74847 C -1.24585 -1.97069 -0.56042 C -2.56537 -2.11793 -1.01991 C -0.56731 -3.18463 -0.33371 C -3.17364 -3.3435 -1.23543 C -1.15159 -4.4246 -0.54123 C -2.46287 -4.51168 -0.99374 C 0.51107 3.44312 -0.11301 C -0.32355 4.37955 -0.74596 C 1.61415 4.0048 0.56014 C -0.0995 5.74625 -0.72898 C 1.86229 5.36839 0.5932 C 1.00469 6.25003 -0.05426 F 0.70112 -3.18762 0.09849 F -0.45555 -5.53781 -0.30952 F -3.02789 -5.69782 -1.19338 F -4.43103 -3.40328 -1.67072 F -3.30805 -1.02297 -1.27787 F 2.48582 3.22379 1.21295 F -1.41461 3.95583 -1.4146 F -0.93535 6.57284 -1.35523 F 1.23853 7.55799 -0.02668 F 2.92415 5.83804 1.24833 Te -1.56617 1.17473 -0.94008 Br -0.33289 0.85359 -3.39721 Br -2.64488 1.42575 1.59677 SCF Done: E(RB3LYP) = -6766.01463868

  39

PT-NO2-NBu2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.65972 -0.6832 -0.40574 C 0.31807 -0.40934 0.51566 C 0.73573 0.93839 0.70915 C 0.15015 1.93734 -0.02413 H 0.79061 -1.2132 1.07293 H 1.50143 1.16806 1.4453 C -1.23223 -1.98819 -0.72181 C -1.70807 -2.31471 -2.00052 C -1.3236 -2.99792 0.25349 C -2.23467 -3.56264 -2.29989 H -1.62618 -1.58856 -2.80471 C -1.85293 -4.24545 -0.02935 H -1.00637 -2.7881 1.2697 C -2.33453 -4.5745 -1.31865 H -2.53445 -3.75037 -3.32186 H -1.93136 -4.96133 0.77845 C 0.47869 3.35793 0.02279 C -0.47047 4.3495 -0.29568 C 1.77017 3.78612 0.39804 C -0.1599 5.69883 -0.23435 H -1.47964 4.0589 -0.56863 C 2.09247 5.13132 0.47123 H 2.53681 3.05031 0.60977 C 1.12208 6.08014 0.15377 H -0.89568 6.45559 -0.47204 H 3.08521 5.45529 0.75449 Te -1.30136 1.10665 -1.2957 N 1.45946 7.50753 0.22443 O 2.59875 7.81038 0.56616 O 0.58339 8.31834 -0.06122 N -2.88306 -5.82701 -1.57372 C -3.46527 -6.13027 -2.88083 C -4.64746 -7.10526 -2.83643 H -2.69401 -6.51686 -3.56818 H -3.83235 -5.20007 -3.31257 C -5.25843 -7.32646 -4.22504 H -4.33916 -8.07357 -2.4277

  40

H -5.40882 -6.70809 -2.1555 C -6.44626 -8.29114 -4.20848 H -5.57801 -6.36283 -4.64084 H -4.48845 -7.70811 -4.90697 H -6.86278 -8.42798 -5.21016 H -6.15444 -9.27828 -3.83627 H -7.25096 -7.92216 -3.56494 C -2.44741 -6.97319 -0.76799 C -3.38735 -7.36219 0.38275 H -1.44735 -6.76699 -0.3733 H -2.32524 -7.8301 -1.43966 C -2.8511 -8.5402 1.20308 H -3.5447 -6.49667 1.03579 H -4.37363 -7.61209 -0.02147 C -3.78121 -8.94659 2.34839 H -2.68883 -9.40179 0.54274 H -1.86378 -8.2851 1.60852 H -3.37303 -9.78754 2.91578 H -3.93543 -8.12006 3.04911 H -4.76526 -9.2473 1.97529 SCF Done: E(RB3LYP) = -1199.58748717

  41

PT-NO2-NBu2-Br2 (gas phase, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.61959 -0.78428 -0.33597 C 0.28841 -0.4488 0.61245 C 0.67501 0.92673 0.79796 C 0.14045 1.91121 0.03939 H 0.74719 -1.21915 1.22496 H 1.39922 1.17449 1.56983 C -1.20721 -2.05974 -0.66413 C -1.73643 -2.34541 -1.9346 C -1.246 -3.10507 0.2814 C -2.25333 -3.58552 -2.25776 H -1.69637 -1.59685 -2.72053 C -1.76411 -4.34614 -0.02586 H -0.89497 -2.92627 1.29196 C -2.29043 -4.63968 -1.31192 H -2.596 -3.73525 -3.2716 H -1.79948 -5.0894 0.75857 C 0.45369 3.33333 0.03708 C -0.52523 4.30154 -0.25015 C 1.75659 3.76982 0.34765 C -0.22787 5.65552 -0.20803 H -1.54501 3.99744 -0.46061 C 2.06428 5.12033 0.39749 H 2.53877 3.0407 0.52245 C 1.06623 6.05014 0.11728 H -0.98251 6.40251 -0.41473 H 3.06483 5.46029 0.62919 N 1.39 7.48773 0.16485 O 2.53423 7.80323 0.4708 O 0.49612 8.28205 -0.10271 N -2.81119 -5.88671 -1.59376 C -3.40932 -6.19014 -2.897 C -4.63712 -7.10634 -2.83461 H -2.65158 -6.63122 -3.56342 H -3.72624 -5.25681 -3.35695 C -5.24807 -7.33255 -4.22266 H -4.37656 -8.07742 -2.40056 H -5.38336 -6.65742 -2.16942

  42

C -6.47273 -8.2495 -4.1926 H -5.527 -6.3664 -4.66087 H -4.4895 -7.75875 -4.89082 H -6.889 -8.3901 -5.19367 H -6.22123 -9.23942 -3.79917 H -7.26547 -7.83625 -3.56147 C -2.42462 -7.03921 -0.7705 C -3.38094 -7.37682 0.38321 H -1.41565 -6.87173 -0.38093 H -2.34055 -7.90453 -1.43534 C -2.88744 -8.56467 1.21594 H -3.5082 -6.49974 1.02682 H -4.37469 -7.59546 -0.02012 C -3.83026 -8.9215 2.36745 H -2.75952 -9.43906 0.56526 H -1.89034 -8.34253 1.61673 H -3.45279 -9.77041 2.94388 H -3.95142 -8.08153 3.05844 H -4.82561 -9.18933 1.9996 Te -1.23941 1.0284 -1.33039 Br 0.81298 0.74229 -3.17369 Br -3.27961 1.2879 0.53029 SCF Done: E(RB3LYP) = -6347.89367258

  43

Geometry Coordinates for Structures Used in Mechanistic Study

Reactants PT and Br2 (gas phase B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.48211 -0.81618 -0.34368 C 0.69876 -0.50394 0.26795 C 1.0811 0.86656 0.39293 C 0.25554 1.83928 -0.09551 H 1.35314 -1.28986 0.63547 H 2.00905 1.1316 0.89251 C -1.04876 -2.15464 -0.53604 C -1.81638 -2.47626 -1.66766 C -0.83165 -3.16434 0.41878 C -2.33788 -3.75339 -1.84317 H -1.98296 -1.72289 -2.43194 C -1.34781 -4.44272 0.23857 H -0.27601 -2.93244 1.32097 C -2.10421 -4.74511 -0.89256 H -2.9232 -3.97597 -2.72973 H -1.16926 -5.20311 0.99247 H -2.51154 -5.74153 -1.02903 C 0.49387 3.28579 -0.08241 C -0.55962 4.20741 0.03632 C 1.80166 3.7934 -0.18509 C -0.31766 5.57663 0.061 H -1.57816 3.84478 0.13812 C 2.04281 5.16229 -0.15293 H 2.62999 3.1059 -0.31741 C 0.98529 6.06219 -0.03025 H -1.15028 6.26599 0.15877 H 3.06127 5.52838 -0.23745 H 1.17423 7.13053 -0.0112 Te -1.44835 0.9505 -0.94944 Br -4.89632 5.65065 -3.59326 Br -6.88852 5.38259 -2.40758 SCF Done: E(RB3LYP) = -5773.36708274

  44

Int1 (gas phase, B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.58553 -0.59983 -0.44619 C 0.14 -0.22452 0.64077 C 0.59122 1.13405 0.76281 C 0.28209 2.03786 -0.20452 H 0.39398 -0.95156 1.40728 H 1.1579 1.44239 1.63717 C -1.1634 -1.91552 -0.72891 C -1.26395 -2.41102 -2.03891 C -1.62789 -2.7249 0.32295 C -1.79444 -3.67162 -2.28867 H -0.8991 -1.81419 -2.86966 C -2.15315 -3.98698 0.07132 H -1.60223 -2.34567 1.33855 C -2.23857 -4.46722 -1.23453 H -1.85773 -4.03434 -3.30938 H -2.51196 -4.59184 0.8978 H -2.656 -5.44941 -1.42958 C 0.68127 3.44623 -0.27577 C -0.18247 4.43106 -0.78171 C 1.95085 3.84416 0.1783 C 0.20453 5.76612 -0.82103 H -1.1792 4.15554 -1.1119 C 2.33321 5.18044 0.14121 H 2.64718 3.0943 0.53808 C 1.46271 6.14747 -0.35871 H -0.48338 6.51145 -1.20652 H 3.31959 5.46555 0.49286 H 1.7639 7.18927 -0.39151 Te -0.83364 1.07206 -1.72051 Br -6.00644 2.50668 -0.24343 Br -3.73326 1.86385 -0.86736 SCF Done: E(RB3LYP) = -5773.37712090

  45

TS1 (gas phase, B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.58524 -0.69493 -0.40781 C 0.30698 -0.34062 0.54949 C 0.70606 1.0379 0.70377 C 0.18719 2.00387 -0.09547 H 0.73741 -1.09808 1.19858 H 1.42195 1.30308 1.47617 C -1.171 -2.0039 -0.68712 C -1.5327 -2.38789 -1.98889 C -1.37607 -2.92125 0.35931 C -2.06321 -3.64763 -2.24026 H -1.37692 -1.70622 -2.82025 C -1.90035 -4.18214 0.10362 H -1.15026 -2.62945 1.37893 C -2.24564 -4.55154 -1.19581 H -2.33313 -3.92337 -3.25398 H -2.05683 -4.87321 0.92518 H -2.66423 -5.5329 -1.39112 C 0.51299 3.42358 -0.17509 C -0.41102 4.36877 -0.65052 C 1.78128 3.87271 0.24538 C -0.08512 5.71946 -0.68581 H -1.40578 4.08077 -0.98043 C 2.09749 5.22353 0.21308 H 2.52707 3.15671 0.57359 C 1.16521 6.15313 -0.25125 H -0.82266 6.42419 -1.05322 H 3.07992 5.55168 0.53653 H 1.41802 7.20778 -0.28197 Te -1.15977 1.06432 -1.47111 Br -3.94523 4.45113 -2.20757 Br -3.50034 1.55034 -0.32566 SCF Done: E(RB3LYP) = -5773.31955340

  46

Int2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.69773 -0.68474 -0.38949 C 0.32345 -0.33393 0.41133 C 0.69085 1.06883 0.51759 C 0.05572 2.03842 -0.17159 H 0.8906 -1.07028 0.97664 H 1.50372 1.35395 1.18165 C -1.22852 -2.02416 -0.62268 C -1.73361 -2.40803 -1.87655 C -1.24973 -2.9719 0.4176 C -2.22011 -3.69295 -2.08968 H -1.72498 -1.70393 -2.70274 C -1.73887 -4.25409 0.20274 H -0.90684 -2.68534 1.40585 C -2.22386 -4.62228 -1.05207 H -2.59826 -3.96731 -3.06891 H -1.75308 -4.96665 1.02117 H -2.60995 -5.62272 -1.21644 C 0.39908 3.46399 -0.18397 C -0.5064 4.44161 0.25213 C 1.68523 3.85911 -0.58701 C -0.12504 5.7774 0.30188 H -1.50455 4.1525 0.55584 C 2.06077 5.19724 -0.53851 H 2.38392 3.11068 -0.94646 C 1.15588 6.1589 -0.09294 H -0.83477 6.5236 0.64247 H 3.05712 5.48905 -0.85415 H 1.44607 7.20402 -0.05958 Te -1.40016 1.10774 -1.48403 Br -2.50179 3.59789 -2.40224 Br -3.56598 0.82427 -0.0971 SCF Done: E(RB3LYP) = -5773.35577310

  47

TS2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.70699 -0.71304 -0.38861 C 0.08205 -0.3349 0.62984 C 0.44632 1.06936 0.76569 C 0.04354 2.00972 -0.10992 H 0.45461 -1.04668 1.36406 H 1.04284 1.37927 1.62049 C -1.2453 -2.03648 -0.678 C -1.61518 -2.90246 0.36877 C -1.41858 -2.48396 -1.99963 C -2.11368 -4.17072 0.1001 H -1.53273 -2.56148 1.3951 C -1.91581 -3.75501 -2.26522 H -1.13713 -1.84339 -2.8296 C -2.26401 -4.60428 -1.21734 H -2.39733 -4.82076 0.92149 H -2.03181 -4.08157 -3.29332 H -2.6585 -5.59336 -1.42476 C 0.37882 3.434 -0.08227 C -0.61242 4.42544 -0.1251 C 1.72213 3.8231 0.04324 C -0.26885 5.76724 -0.02143 H -1.65326 4.14365 -0.23132 C 2.06153 5.16772 0.14332 H 2.49859 3.06544 0.04154 C 1.06671 6.14271 0.11256 H -1.04619 6.52295 -0.05571 H 3.1042 5.45429 0.23354 H 1.33184 7.19261 0.18254 Te -1.08364 1.04457 -1.71163 Br -0.68308 3.33796 -3.45869 Br -3.43552 1.39255 -0.67947 SCF Done: E(RB3LYP) = -5773.35242726

  48

Product PT-Br2 (gas phase, B3LYP, 6-311g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.63919 -0.64962 -0.4497 C 0.51778 -0.32735 0.15916 C 0.90773 1.06003 0.32656 C 0.11374 2.05639 -0.10902 H 1.17435 -1.11524 0.51848 H 1.84516 1.29686 0.82263 C -1.25319 -1.95921 -0.65056 C -1.8977 -2.28937 -1.85367 C -1.19532 -2.92096 0.37216 C -2.45247 -3.55089 -2.03318 H -1.92801 -1.56937 -2.66531 C -1.74983 -4.18221 0.1857 H -0.74243 -2.66151 1.32255 C -2.37963 -4.50153 -1.01585 H -2.93854 -3.79372 -2.97213 H -1.70488 -4.91164 0.98767 H -2.81839 -5.48378 -1.15641 C 0.34348 3.49857 -0.11027 C -0.68328 4.40334 0.20464 C 1.61735 4.00238 -0.4226 C -0.43664 5.77085 0.22329 H -1.66637 4.03162 0.47567 C 1.85859 5.37147 -0.39975 H 2.40512 3.31629 -0.71307 C 0.83412 6.25958 -0.07735 H -1.23793 6.45631 0.47813 H 2.84522 5.74636 -0.65129 H 1.02257 7.32798 -0.06786 Te -1.63296 1.17786 -1.01517 Br -0.31982 1.17445 -3.44557 Br -2.93151 1.18075 1.42429 SCF Done: E(RB3LYP) = -5773.38662216

  49

Reactants PT and Br2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.47433 -0.82067 -0.3378 C 0.71107 -0.51386 0.27158 C 1.09541 0.85657 0.40221 C 0.2673 1.83229 -0.08035 H 1.36502 -1.29997 0.63906 H 2.02846 1.11553 0.89519 C -1.04238 -2.15994 -0.5302 C -1.83316 -2.47367 -1.64918 C -0.80181 -3.17861 0.41097 C -2.35549 -3.75188 -1.82583 H -2.02378 -1.71513 -2.40239 C -1.31795 -4.45832 0.22932 H -0.22363 -2.95783 1.3016 C -2.09866 -4.75287 -0.88908 H -2.9593 -3.96721 -2.70153 H -1.12037 -5.22494 0.97189 H -2.50576 -5.74915 -1.02628 C 0.51297 3.27895 -0.06427 C -0.53651 4.20632 0.05631 C 1.82458 3.77984 -0.1653 C -0.28706 5.57567 0.08358 H -1.55844 3.85239 0.15293 C 2.07345 5.14874 -0.12993 H 2.6515 3.09011 -0.29399 C 1.01968 6.05508 -0.00643 H -1.11612 6.26903 0.18193 H 3.09391 5.50913 -0.21299 H 1.21428 7.12224 0.01443 Te -1.43839 0.94919 -0.93165 Br -5.2105 5.77179 -3.88362 Br -7.03794 5.47329 -2.46264 SCF Done: E(RB3LYP) = -5773.38307911

  50

Int1 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.6072 -0.59197 -0.44444 C 0.10597 -0.21111 0.64643 C 0.55894 1.15111 0.7689 C 0.26729 2.05416 -0.20287 H 0.34887 -0.93011 1.42359 H 1.12073 1.45319 1.6482 C -1.18698 -1.90509 -0.73181 C -1.29749 -2.39053 -2.04558 C -1.63769 -2.72409 0.32011 C -1.82202 -3.65406 -2.29983 H -0.9495 -1.78651 -2.87798 C -2.15694 -3.98883 0.0637 H -1.59974 -2.35692 1.33959 C -2.25199 -4.46028 -1.2463 H -1.89249 -4.00932 -3.32247 H -2.50338 -4.60201 0.88908 H -2.6644 -5.44384 -1.44437 C 0.68159 3.45743 -0.28067 C -0.13483 4.43504 -0.87335 C 1.91761 3.86001 0.25837 C 0.26148 5.76847 -0.91409 H -1.10324 4.1595 -1.27895 C 2.30955 5.19438 0.22001 H 2.58136 3.11912 0.69013 C 1.48442 6.15494 -0.36615 H -0.39008 6.50695 -1.36908 H 3.26847 5.4826 0.63813 H 1.79398 7.19408 -0.39956 Te -0.82971 1.07897 -1.73493 Br -5.93557 2.32888 -0.11213 Br -3.58094 1.75567 -0.86138 SCF Done: E(RB3LYP) = -5773.39612411

  51

TS1 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.5706 -0.73398 -0.40913 C 0.2399 -0.34395 0.5969 C 0.623 1.04894 0.74919 C 0.17201 1.99873 -0.09891 H 0.61341 -1.07537 1.30748 H 1.27525 1.32944 1.57092 C -1.15534 -2.03688 -0.70086 C -1.41652 -2.45224 -2.01747 C -1.45265 -2.91875 0.35575 C -1.93624 -3.7162 -2.27406 H -1.19391 -1.79659 -2.85391 C -1.96679 -4.18311 0.09378 H -1.2988 -2.60222 1.38106 C -2.21077 -4.5869 -1.22001 H -2.12634 -4.0202 -3.29741 H -2.19455 -4.84904 0.91897 H -2.62143 -5.57053 -1.41976 C 0.5115 3.41483 -0.18942 C -0.42516 4.37345 -0.61171 C 1.80083 3.84197 0.18511 C -0.08664 5.72182 -0.64216 H -1.43796 4.09478 -0.88906 C 2.13033 5.19176 0.15534 H 2.54707 3.11264 0.48028 C 1.18879 6.13595 -0.25862 H -0.83039 6.44352 -0.96055 H 3.12816 5.50592 0.44232 H 1.45055 7.18819 -0.28717 Te -1.00333 1.00204 -1.60444 Br -4.2417 5.15884 -1.641 Br -3.35557 1.42297 -0.76118 SCF Done: E(RB3LYP) = -5773.36218876

  52

Int2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.66417 -0.69965 -0.39584 C 0.34397 -0.33849 0.41781 C 0.70116 1.06744 0.52841 C 0.05212 2.03288 -0.1549 H 0.90394 -1.07044 0.99379 H 1.51421 1.35446 1.19055 C -1.2085 -2.03438 -0.62373 C -1.70468 -2.42271 -1.88037 C -1.24169 -2.97334 0.42527 C -2.1962 -3.70792 -2.08835 H -1.68495 -1.72664 -2.71304 C -1.73421 -4.25612 0.21436 H -0.90018 -2.68498 1.41327 C -2.21233 -4.63019 -1.04292 H -2.56666 -3.98772 -3.06873 H -1.75698 -4.96312 1.03708 H -2.60108 -5.63006 -1.20335 C 0.38217 3.46195 -0.17942 C -0.53657 4.43558 0.23925 C 1.67191 3.86349 -0.56641 C -0.16556 5.77538 0.28872 H -1.53613 4.14208 0.53604 C 2.03695 5.20614 -0.52036 H 2.38231 3.11849 -0.9086 C 1.11918 6.16471 -0.09136 H -0.88332 6.51803 0.62017 H 3.03554 5.50282 -0.82354 H 1.40198 7.21164 -0.05775 Te -1.37593 1.07676 -1.47108 Br -2.53082 3.63949 -2.5997 Br -3.51728 0.91531 -0.06453 SCF Done: E(RB3LYP) = -5773.38064498

  53

TS2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.70344 -0.7165 -0.3853 C 0.09183 -0.34255 0.63224 C 0.46546 1.05855 0.77544 C 0.04983 2.00384 -0.08998 H 0.4575 -1.06113 1.36118 H 1.07567 1.35698 1.62394 C -1.25871 -2.03297 -0.67867 C -1.6027 -2.90445 0.37315 C -1.45946 -2.47056 -1.99972 C -2.10314 -4.17373 0.10725 H -1.49402 -2.57327 1.39998 C -1.9607 -3.74193 -2.26188 H -1.19968 -1.82682 -2.83411 C -2.28304 -4.59898 -1.21049 H -2.36577 -4.82937 0.93079 H -2.09844 -4.06223 -3.28898 H -2.67908 -5.58785 -1.41502 C 0.38244 3.42996 -0.07098 C -0.61481 4.41689 -0.08997 C 1.72689 3.82368 0.02947 C -0.27571 5.76147 0.00954 H -1.65772 4.13223 -0.17038 C 2.06207 5.17138 0.12484 H 2.50665 3.06986 0.01811 C 1.06218 6.14323 0.11596 H -1.05716 6.51364 -0.00174 H 3.10494 5.46185 0.1961 H 1.32385 7.19388 0.18447 Te -1.06376 1.02462 -1.67839 Br -0.59484 3.36948 -3.63449 Br -3.42396 1.4153 -0.72211 SCF Done: E(RB3LYP) = -5773.37857083

  54

Product PT-Br2 (CHCl3 PCM, B3LYP, 6-311+g(d)/LANL2DZ) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.65387 -0.64502 -0.47961 C 0.55505 -0.33821 0.03532 C 0.95737 1.0415 0.21173 C 0.13139 2.05117 -0.13387 H 1.24352 -1.12986 0.31589 H 1.93335 1.25708 0.6364 C -1.28355 -1.94775 -0.66299 C -2.21199 -2.18112 -1.69111 C -0.94492 -3.01624 0.18885 C -2.76583 -3.4432 -1.87791 H -2.48086 -1.38366 -2.37685 C -1.50027 -4.27625 -0.00148 H -0.26179 -2.85081 1.01423 C -2.41288 -4.49602 -1.03442 H -3.47338 -3.60339 -2.68422 H -1.23199 -5.08555 0.66931 H -2.84981 -5.47861 -1.17632 C 0.36089 3.49088 -0.11304 C -0.69524 4.40494 0.0365 C 1.6713 3.99486 -0.21973 C -0.45113 5.7728 0.10033 H -1.71588 4.05006 0.13989 C 1.91147 5.36221 -0.1546 H 2.49943 3.31308 -0.37612 C 0.85259 6.25768 0.005 H -1.2814 6.4595 0.22472 H 2.92755 5.73136 -0.24514 H 1.04219 7.32478 0.048 Te -1.68233 1.19417 -0.90979 Br -0.54639 1.26715 -3.45431 Br -2.76546 1.11714 1.65751 SCF Done: E(RB3LYP) = -5773.41023020

  55

Figure S1 IRC path for gas-phase optimized structure of TS1-2 and the associated geometries.

The “reactant” and “product” geometries from IRC optimize to the geometries of Int1 and Int2,

respectively, in a few steps.

  56

Figure S2 IRC path for gas-phase optimized structure of TS2-P and the associated geometries.

The “reactant” and “product” geometries from IRC optimize to the geometries of Int2 and PT-

Br2, respectively, in a few steps.

  57

Density Functional Theory Data for Chapter 5

Geometry Coordinates and Energies for Minimum Energy Structures

Geometry Optimizations: Chloroform PCM, B3LYP, 6-311+g(d)/LANL2DZ for Te

Energies were calculated from single point energy (chloroform PCM, B3LYP, 6-311+g(2df, 2p)/SDD for Te) with added zero-point energy correction from scaled frequency calculation

PT Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.66029 -0.56552 -0.44416 C 0.53359 -0.36265 0.19118 C 1.00674 0.97309 0.379 C 0.25242 2.01948 -0.07526 H 1.12735 -1.20492 0.53586 H 1.94773 1.1503 0.89264 C -1.31407 -1.8558 -0.6933 C -2.08154 -2.08456 -1.84847 C -1.18126 -2.91089 0.2287 C -2.6851 -3.31787 -2.07799 H -2.18883 -1.29588 -2.58701 C -1.77919 -4.14583 -0.00544 H -0.62284 -2.75202 1.14471 C -2.53528 -4.35662 -1.1591 H -3.26861 -3.46907 -2.98045 H -1.66493 -4.94239 0.72293 H -3.00602 -5.31772 -1.33756 C 0.59197 3.44513 0.00082 C -0.39639 4.43333 0.15054 C 1.93428 3.86279 -0.06958 C -0.05941 5.78143 0.23443 H -1.43988 4.1425 0.22504 C 2.27063 5.21023 0.02231 H 2.71615 3.12629 -0.21908 C 1.27655 6.17771 0.17369 H -0.84279 6.52285 0.35427 H 3.31302 5.50666 -0.0383

H 1.53987 7.22821 0.23864 Te -1.49588 1.28575 -0.98056 Total Energy: -624.9674468 Hartrees

  58

PT-O Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.62609 -0.56865 -0.46916 C 0.54828 -0.34879 0.15881 C 1.03248 1.01048 0.35921 C 0.31124 2.06482 -0.07589 H 1.14847 -1.17638 0.52975 H 1.97105 1.15637 0.889 C -1.30914 -1.84002 -0.69263 C -2.13469 -2.04717 -1.81156 C -1.15014 -2.90245 0.21862 C -2.75789 -3.27285 -2.026 H -2.27813 -1.25271 -2.53735 C -1.7724 -4.12648 0.00136 H -0.55424 -2.75642 1.11265 C -2.57807 -4.31924 -1.12245 H -3.38568 -3.40875 -2.90028 H -1.64028 -4.929 0.71966 H -3.06841 -5.27293 -1.28625 C 0.64921 3.48639 0.00342 C -0.35831 4.45948 0.12457 C 1.99025 3.91275 -0.02256 C -0.03535 5.80894 0.23521 H -1.39978 4.15646 0.16278 C 2.30909 5.26225 0.08843 H 2.78332 3.18375 -0.14922 C 1.29844 6.21644 0.21726 H -0.82808 6.54259 0.33726 H 3.3489 5.5716 0.06172 H 1.549 7.26887 0.29847 Te -1.40879 1.32848 -1.16402 O -2.92404 1.68308 -0.13765 Total Energy: -700.1470503 Hartrees

  59

PT-O2 Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.60901 -0.65517 -0.39733 C 0.54547 -0.38828 0.23826 C 1.03415 0.98409 0.4258 C 0.35631 2.05227 -0.02945 H 1.15687 -1.19663 0.62803 H 1.97115 1.11536 0.95893 C -1.29723 -1.91394 -0.64668 C -2.15841 -2.063 -1.74684 C -1.09765 -3.01423 0.20876 C -2.78629 -3.27893 -1.996 H -2.32385 -1.23396 -2.42793 C -1.7254 -4.2273 -0.04641 H -0.46667 -2.91073 1.08444 C -2.5713 -4.36523 -1.14887 H -3.44366 -3.37593 -2.85304 H -1.56628 -5.06423 0.62516 H -3.06561 -5.31153 -1.34042 C 0.6735 3.4731 0.00062 C -0.3439 4.44227 -0.00324 C 2.01385 3.90076 0.04764 C -0.03257 5.79666 0.05684 H -1.38631 4.1401 -0.03066 C 2.31898 5.255 0.10978 H 2.81517 3.17118 0.01397 C 1.29838 6.20803 0.11475 H -0.83159 6.52989 0.05745 H 3.35683 5.56931 0.13929 H 1.54056 7.26455 0.15512 O -2.95077 1.69277 -0.11939 Te -1.40318 1.25834 -0.9779 O -1.42997 1.51526 -2.7819 Total Energy: -775.3233762 Hartrees

  60

IntA Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C 1.26828 0.98548 -0.20864 C 0.40704 2.00911 -0.29336 H 2.26295 1.12316 0.20955 C -1.30761 -1.8111 -0.97587 C -1.27851 -2.805 -1.9606 C -2.11501 -1.97875 0.15782 C -2.03752 -3.96344 -1.80474 H -0.65427 -2.67159 -2.83682 C -2.86968 -3.13932 0.30718 H -2.15824 -1.19884 0.90988 C -2.83326 -4.13354 -0.67193 H -2.00706 -4.73297 -2.56919 H -3.48992 -3.26591 1.1883 H -3.42318 -5.03631 -0.55212 C 0.66883 3.4151 0.04234 C -0.31329 4.19481 0.67591 C 1.9096 4.00393 -0.25601 C -0.05272 5.51902 1.01756 H -1.27322 3.75465 0.92576 C 2.16433 5.32942 0.08456 H 2.66675 3.425 -0.77382 C 1.18518 6.091 0.72327 H -0.8183 6.10428 1.51592 H 3.12549 5.77063 -0.15808 H 1.38385 7.12489 0.9853 Te -1.48641 1.40608 -1.17933 O -2.68889 1.40839 0.2382 C -0.4973 -0.58056 -1.13185 C 0.87965 -0.37306 -0.64273 H 1.42235 -1.22058 -0.23679 O 0.56176 -0.55005 -2.07031 Total Energy: -775.3647605 Hartrees

  61

IntB Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.26591 -1.74682 -0.98167 C -1.22598 -2.89944 -1.77491 C -2.27296 -1.60058 -0.01754 C -2.17504 -3.90352 -1.59466 H -0.44721 -3.00902 -2.52111 C -3.21909 -2.60778 0.15569 H -2.32282 -0.69614 0.57795 C -3.1726 -3.76016 -0.63018 H -2.13558 -4.79715 -2.2089 H -3.99563 -2.49104 0.90432 H -3.91119 -4.54286 -0.4915 C 0.83454 3.35909 -0.08603 C -0.10357 3.67362 0.9072 C 1.75305 4.32891 -0.50491 C -0.10684 4.94172 1.48291 H -0.83379 2.93345 1.21383 C 1.74481 5.59499 0.07693 H 2.47557 4.08488 -1.2754 C 0.81625 5.90395 1.07096 H -0.83287 5.17888 2.25341 H 2.46349 6.34046 -0.24731 H 0.81139 6.89044 1.5228 Te -0.96383 1.33829 -1.82976 O -2.34938 1.69053 -0.64624 C -0.26244 -0.67408 -1.17801 C 1.0233 -0.53954 -0.46292 H 1.31773 -1.31756 0.23506 O 0.95636 -0.98003 -1.83693 C 0.84026 2.01284 -0.70658 C 1.58728 0.83316 -0.22304 H 2.24962 0.94727 0.62993 O 2.00372 1.57332 -1.39086 Total Energy: -850.5805354 Hartrees

  62

IntC Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.39765 -0.7447 -1.11838 C 0.89231 -0.41711 -0.49482 C 1.21365 0.98455 -0.1144 H 1.4233 -1.21121 0.0175 H 2.16507 1.15265 0.38319 C -1.21247 -1.96753 -0.98868 C -1.29423 -2.86014 -2.0633 C -1.9104 -2.22972 0.19703 C -2.06045 -4.01673 -1.94475 H -0.75181 -2.65238 -2.97873 C -2.67596 -3.38664 0.30656 H -1.85504 -1.53572 1.02936 C -2.75276 -4.28045 -0.76273 H -2.11851 -4.71042 -2.77651 H -3.21259 -3.59058 1.22667 H -3.35151 -5.18066 -0.67406 C 0.58172 3.43617 -0.10269 C -0.49178 4.25985 0.27317 C 1.86319 4.00155 -0.22445 C -0.28333 5.60815 0.54508 H -1.48935 3.84494 0.37738 C 2.06495 5.35037 0.04738 H 2.69434 3.38803 -0.55375 C 0.99406 6.15698 0.43484 H -1.12085 6.23014 0.84137 H 3.05755 5.77539 -0.05655 H 1.15316 7.21009 0.64045 O 0.72851 -0.68749 -1.93968 Te -1.41633 1.24007 -1.25801 O -1.6512 1.87791 -2.94917 O -2.84416 1.42398 -0.1385 C 0.38272 2.00826 -0.34964 Total Energy: -850.5371495 Hartrees

  63

IntC’ + TeO2 + CBA (optimized from TSA-C IRC product structure) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C 0.347 -0.49239 3.45617 C 1.00849 -0.32233 2.24683 H 0.26167 0.24012 4.2446 C 0.28005 -3.80491 1.83178 C -0.51505 -4.76597 2.47965 C 0.98859 -4.17647 0.67723 C -0.5947 -6.06273 1.98575 H -1.08056 -4.49722 3.36514 C 0.90095 -5.47558 0.186 H 1.60854 -3.44793 0.1688 C 0.1123 -6.42391 0.83708 H -1.21469 -6.79264 2.49528 H 1.45375 -5.74828 -0.70679 H 0.04645 -7.43601 0.45231 C 1.71992 0.78973 1.64397 C 2.253 0.68385 0.34696 C 1.90016 1.98597 2.36043 C 2.94767 1.74925 -0.21349 H 2.12101 -0.23191 -0.21636 C 2.59716 3.04574 1.79323 H 1.50063 2.08885 3.36271 C 3.12315 2.93274 0.50552 H 3.3528 1.65662 -1.21545 H 2.72891 3.9625 2.35747 H 3.66627 3.76196 0.06502 O -1.16052 3.21636 -0.45496 C -1.37374 2.17278 -1.23915 O -1.72108 1.07367 -0.81812 C -1.15549 2.44563 -2.68958 C -1.36157 1.40083 -3.59693 C -0.75646 3.70552 -3.14785 C -1.16195 1.63324 -4.94996 H -1.67261 0.42911 -3.23594 C -0.56426 3.9167 -4.51043 H -0.59992 4.50938 -2.44055 C -0.76475 2.88185 -5.42279

Cl -1.41686 0.31942 -6.0964 H -0.25648 4.89211 -4.87055 H -0.61613 3.04209 -6.48394 O -1.67653 2.34908 1.94704 H -1.31863 2.95118 0.50675 Te -2.11602 0.57314 2.07621 O -3.13675 0.45145 3.57427 C -0.03264 -1.86485 3.53045 H -0.54371 -2.34105 4.35209 C 0.3704 -2.45277 2.36243 O 0.99582 -1.50813 1.5785 Total Energy: -1731.166092 Hartrees

  64

IntC’ + TeO2 + CBA (optimized from TSPTO2-C IRC product structure) Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.77945 -0.8632 1.74795 C -0.66717 -0.58423 3.09663 H -1.46316 -0.63227 3.82458 O 0.43739 -0.63177 1.15467 H 0.3039 0.72564 -0.43862 O -0.56209 2.72582 0.33286 C -0.22694 2.50921 -0.8122 O 0.27087 1.32112 -1.20853 C -0.31335 3.50276 -1.91803 C -0.79774 4.77887 -1.60918 C 0.07179 3.19444 -3.2272 C -0.88775 5.72786 -2.61674 H -1.09423 5.01019 -0.59429 C -0.02867 4.16247 -4.2226 H 0.446 2.20662 -3.4618 C -0.5086 5.43688 -3.92541 H 0.26811 3.92848 -5.23888 H -0.58716 6.193 -4.69731 Cl -1.49432 7.33599 -2.23331 C 0.66871 -0.14315 3.32624 H 1.09508 0.13368 4.27745 C 1.32101 -0.19269 2.12694 O 0.23713 -3.50632 5.10855 C -1.87932 -1.28413 0.89735 C -1.64308 -1.80044 -0.38849 C -3.2026 -1.18435 1.35985 C -2.70719 -2.19561 -1.19156 H -0.62791 -1.89714 -0.75569 C -4.25993 -1.58844 0.55409 H -3.40576 -0.77584 2.34322 C -4.01774 -2.09296 -0.72442 H -2.5123 -2.59109 -2.18262 H -5.2764 -1.50339 0.92251 H -4.84556 -2.40412 -1.35242 C 2.6868 0.08871 1.71032 C 3.18778 -0.39168 0.48901

C 3.53152 0.84539 2.54063 C 4.49928 -0.11994 0.11081 H 2.55558 -0.98719 -0.15925 C 4.84219 1.10722 2.15955 H 3.15735 1.24131 3.47825 C 5.33172 0.62793 0.9429 H 4.87264 -0.49812 -0.83495 H 5.48135 1.69518 2.80954 H 6.35366 0.83782 0.64592 Te -0.14251 -3.64712 3.33397 O -1.79499 -4.38965 3.16485 Total Energy: -1731.149562 Hartrees

  65

IntD Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.21857 -0.80281 -1.19923 C 1.03015 -0.54016 -0.45543 C 1.55145 0.86696 -0.26112 C 0.83116 2.03551 -0.8033 H 1.34713 -1.27086 0.28156 H 2.1992 1.02014 0.59595 C -1.18765 -1.89918 -0.9975 C -1.15093 -3.01588 -1.8403 C -2.14999 -1.81677 0.01689 C -2.06287 -4.05199 -1.65569 H -0.40631 -3.07303 -2.6259 C -3.05865 -2.85569 0.19371 H -2.19284 -0.94411 0.65971 C -3.01681 -3.97359 -0.64104 H -2.02958 -4.91904 -2.30655 H -3.80076 -2.79191 0.98202 H -3.72754 -4.78113 -0.50121 C 0.76837 3.40833 -0.26428 C -0.00943 3.69325 0.86508 C 1.47525 4.43269 -0.90515 C -0.06899 4.99498 1.35369 H -0.56597 2.90383 1.35897 C 1.41278 5.73184 -0.40862 H 2.07504 4.20808 -1.77988 C 0.64059 6.01499 0.71829 H -0.6695 5.21284 2.23011 H 1.96494 6.5234 -0.90352 H 0.59084 7.02888 1.10077 O 1.01989 -1.0404 -1.81323 O 1.98031 1.56417 -1.45505 Te -0.96683 1.19991 -1.83764 O -0.98601 1.45839 -3.64382 O -2.4904 1.61783 -0.92681 Total Energy: -925.7490498 Hartrees

  66

(Z)-ED Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.65511 0.65552 0.06373 C -1.03872 -0.24033 -0.95244 H -2.64299 0.42308 0.44234 C 1.54823 1.87576 0.80952 C 1.52876 0.91361 1.82743 C 2.76284 2.48277 0.45879 C 2.7053 0.56389 2.48563 H 0.59626 0.43385 2.10362 C 3.93648 2.13086 1.11425 H 2.7694 3.22576 -0.33011 C 3.90935 1.17095 2.12958 H 2.68355 -0.18225 3.27276 H 4.87374 2.60176 0.8371 H 4.82635 0.89724 2.64124 C -1.841 -1.36808 -1.51604 C -1.158 -2.39171 -2.19219 C -3.23924 -1.43281 -1.41996 C -1.853 -3.45964 -2.74553 H -0.0788 -2.33495 -2.27035 C -3.93622 -2.49666 -1.98891 H -3.79891 -0.64793 -0.92584 C -3.24558 -3.51373 -2.64596 H -1.31335 -4.24992 -3.25654 H -5.01816 -2.53013 -1.91887 H -3.78951 -4.34553 -3.08135 C 0.30724 2.28612 0.09737 C -1.02101 1.72978 0.54683 H -1.51843 2.3395 1.29891 O 0.30077 3.15282 -0.76267 O 0.12258 -0.06188 -1.30177 Total Energy: -767.3815223 Hartrees

TeO2 Symbolic Z-matrix: Charge = 0 Multiplicity = 1 O 0.27439 -0.12292 0.00464 Te 0.60868 -0.50836 1.74406 O 1.09217 1.01845 2.59264 Total Energy: -158.4943553 Hartrees

  67

MCPBA Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -2.51264 -1.51965 0.21572 C -1.12915 -1.50914 0.07366 C -0.46251 -0.30306 -0.16613 C -1.184 0.8939 -0.26157 C -2.56427 0.85775 -0.1144 C -3.242 -0.33531 0.12293 H -3.03171 -2.4533 0.40056 H -0.5574 -2.42583 0.14595 H -0.68253 1.83448 -0.44389 H -4.31964 -0.33795 0.23347 C 1.02199 -0.35761 -0.31018 O 1.70412 -1.34151 -0.20593 O 1.51433 0.88728 -0.57846 O 2.95204 0.84075 -0.70218 H 3.09216 1.70365 -1.12492 Cl -3.47666 2.35857 -0.231 Total Energy: -955.6444637 Hartrees

CBA Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -2.50474 -1.52075 0.20739 C -1.12129 -1.49804 0.06803 C -0.46361 -0.28526 -0.16278 C -1.19396 0.90581 -0.2537 C -2.57442 0.85877 -0.11086 C -3.24298 -0.34088 0.11885 H -3.01795 -2.45889 0.38611 H -0.54196 -2.41048 0.13584 H -0.69175 1.84675 -0.43195 H -4.32094 -0.35267 0.22637 C 1.01735 -0.29819 -0.30718 O 1.70829 -1.29121 -0.23507 Cl -3.49977 2.35285 -0.22334 O 1.53619 0.9278 -0.53193 H 2.49905 0.8418 -0.61443 Total Energy: -880.5005254 Hartrees

  68

Geometry Coordinates and Energies for Transition State Structures

TSPT-PTO Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.75727 -0.33177 -0.50942 C 0.56719 -0.12313 -0.2757 C 1.03351 1.20064 0.03424 C 0.14437 2.23072 0.09417 H 1.26842 -0.95269 -0.28998 H 2.08464 1.36446 0.25484 C -1.41618 -1.59081 -0.86141 C -2.73267 -1.87549 -0.46017 C -0.73003 -2.56167 -1.61516 C -3.33597 -3.08675 -0.78518 H -3.28513 -1.15286 0.13286 C -1.33305 -3.77398 -1.93431 H 0.27249 -2.35259 -1.97139 C -2.63853 -4.04391 -1.52154 H -4.35193 -3.28365 -0.45896 H -0.78618 -4.50501 -2.52102 H -3.10934 -4.98709 -1.7778 C 0.43088 3.63978 0.37856 C -0.49158 4.46243 1.04745 C 1.65807 4.20618 -0.01443 C -0.19519 5.79337 1.32707 H -1.44161 4.05266 1.37715 C 1.95438 5.53546 0.27038 H 2.37334 3.60482 -0.56467 C 1.03006 6.33675 0.94192 H -0.92236 6.40532 1.85064 H 2.90562 5.9509 -0.04628 H 1.26011 7.37481 1.15734 O -2.74157 3.3913 -4.49769 C -2.41615 2.39793 -5.14058 O -1.93493 1.30285 -4.59632 C -2.53262 2.32257 -6.63445

C -2.1725 1.16632 -7.33607 C -3.01452 3.44085 -7.32138 C -2.30382 1.15239 -8.71837 H -1.79927 0.29774 -6.81035 C -3.13673 3.40333 -8.70702 H -3.28905 4.32688 -6.76296 C -2.78195 2.25744 -9.41764 Cl -1.85428 -0.30058 -9.60833 H -3.51028 4.269 -9.24271 H -2.87528 2.22264 -10.49642 O -1.87683 1.50274 -2.90604 H -2.20702 2.43063 -2.94226 Te -1.78914 1.49963 -0.33106 Total Energy: -1580.604973 Hartrees

  69

TSPTO-PTO2 Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -0.6435 -0.2894 -0.58346 C 0.64892 -0.07819 -0.26756 C 1.1253 1.2497 0.11611 C 0.29338 2.3072 0.1686 H 1.35731 -0.90186 -0.2538 H 2.16668 1.35842 0.40901 C -1.31056 -1.5217 -0.99258 C -2.66724 -1.74302 -0.69983 C -0.59677 -2.5252 -1.6738 C -3.28447 -2.93712 -1.05886 H -3.23912 -0.99003 -0.16662 C -1.21809 -3.71658 -2.03021 H 0.44045 -2.3598 -1.94317 C -2.56341 -3.92854 -1.72349 H -4.33082 -3.09201 -0.81861 H -0.65483 -4.47659 -2.56147 H -3.04743 -4.85654 -2.00859 C 0.56283 3.70027 0.51064 C -0.40224 4.48408 1.16638 C 1.80768 4.27989 0.20334 C -0.12368 5.80077 1.51913 H -1.36561 4.0557 1.42456 C 2.08126 5.59606 0.56021 H 2.55244 3.7016 -0.33242 C 1.11775 6.36159 1.21855 H -0.87775 6.38885 2.03116 H 3.04425 6.02945 0.31139 H 1.33089 7.39013 1.48944 O -2.87289 3.29291 -4.52838 C -2.54245 2.2818 -5.15463 O -2.03261 1.22164 -4.59866 C -2.70383 2.18343 -6.64583 C -2.33891 1.02221 -7.33593 C -3.22906 3.27812 -7.33847 C -2.50797 0.97924 -8.71348 H -1.93335 0.17252 -6.80321

C -3.38873 3.21174 -8.71945 H -3.50742 4.16824 -6.7886 C -3.02907 2.06053 -9.41905 Cl -2.05177 -0.48083 -9.58903 H -3.7962 4.0589 -9.26006 H -3.1518 2.00354 -10.49394 O -1.95842 1.57698 -2.81331 H -2.35407 2.46937 -3.00174 Te -1.63891 1.61286 -0.52706 O -2.88457 1.6475 0.83791 Total Energy:-1655.775407 Hartrees

  70

TSPTO2-C Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.28663 -0.70198 0.34192 C -0.51986 0.37601 0.64922 H -0.94412 1.21944 1.18408 O 0.86594 0.22576 -2.1776 H 1.27216 1.12518 -2.09884 O 0.48314 0.61476 -3.91691 C 0.94109 1.81352 -4.1277 O 1.48817 2.50275 -3.26062 C 0.75239 2.31183 -5.53393 C 0.17646 1.49952 -6.51698 C 1.16888 3.60885 -5.84786 C 0.0291 2.00432 -7.80234 H -0.14674 0.49493 -6.27843 C 1.01014 4.09306 -7.14291 H 1.6142 4.2234 -5.07573 C 0.43841 3.29374 -8.13191 H 1.33292 5.09851 -7.38983 H 0.31327 3.66529 -9.14185 Cl -0.69309 0.98679 -9.0466 C 0.87397 0.4372 0.30004 H 1.45346 1.28937 0.64492 C 1.49084 -0.51973 -0.48348 O 0.51478 -3.46489 0.49345 C -2.7016 -0.92104 0.52618 C -3.24722 -2.21967 0.49034 C -3.5691 0.16884 0.76229 C -4.60349 -2.42571 0.70362 H -2.60894 -3.07923 0.31325 C -4.92298 -0.04321 0.97118 H -3.18143 1.18071 0.75974 C -5.44511 -1.33985 0.94549 H -5.00388 -3.43268 0.67773 H -5.57831 0.80335 1.1437 H -6.50583 -1.50027 1.10446 C 2.92741 -0.79218 -0.59094 C 3.47726 -1.30361 -1.77697

C 3.76558 -0.56456 0.51285 C 4.84023 -1.56193 -1.86028 H 2.83762 -1.46923 -2.63595 C 5.13052 -0.82104 0.42082 H 3.34696 -0.2044 1.44618 C 5.67018 -1.32064 -0.7636 H 5.25679 -1.95096 -2.78292 H 5.76899 -0.64264 1.27925 H 6.73308 -1.52632 -0.83154 Te 0.01893 -2.1216 -0.63043 O -0.57972 -2.67043 -2.25338 Total Energy: -1730.940644 Hartrees

  71

TSC’-(Z)-ED Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.09259 -0.71041 0.29925 C -0.63659 0.53979 0.6719 H -1.20938 1.31665 1.15268 O 0.54751 0.32261 -2.19534 H 1.16853 1.08524 -2.18533 O 0.15644 0.69856 -3.93504 C 0.84987 1.74345 -4.27447 O 1.61371 2.34811 -3.51663 C 0.6494 2.18258 -5.70244 C -0.1961 1.47636 -6.56495 C 1.32652 3.31698 -6.15908 C -0.34731 1.9211 -7.87188 H -0.72212 0.59753 -6.21666 C 1.15902 3.74482 -7.47299 H 1.97783 3.85159 -5.47921 C 0.31949 3.04909 -8.34206 H 1.68357 4.62492 -7.82874 H 0.18536 3.37667 -9.36599 Cl -1.41142 1.03369 -8.96326 C 0.70204 0.61814 0.26402 H 1.37261 1.45246 0.40433 C 1.02056 -0.59422 -0.36731 C -2.38135 -1.36479 0.41828 C -2.59185 -2.64703 -0.1193 C -3.44261 -0.72056 1.08003 C -3.83122 -3.26462 0.0054 H -1.78502 -3.15164 -0.63636 C -4.67782 -1.34415 1.2008 H -3.30155 0.26845 1.5011 C -4.87759 -2.61805 0.6644 H -3.98207 -4.25302 -0.41523 H -5.4876 -0.83621 1.71336 H -5.8436 -3.10247 0.75861 C 2.29874 -1.24142 -0.66033 C 2.33351 -2.52316 -1.22955 C 3.50784 -0.58799 -0.37794

C 3.55182 -3.13305 -1.51128 H 1.40663 -3.03561 -1.45697 C 4.72287 -1.20051 -0.6676 H 3.5053 0.39898 0.07149 C 4.75057 -2.47502 -1.23464 H 3.56468 -4.12413 -1.95247 H 5.64985 -0.68291 -0.44471 H 5.69909 -2.95188 -1.45775 O -0.08631 -1.40258 -0.29977 Total Energy: -1647.771733 Hartrees

  72

TSPTO-A Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.30064 -0.67641 0.30025 C -0.59071 0.431 0.64274 H -1.06363 1.28066 1.12694 O 0.80233 0.35083 -2.1259 H 1.39151 1.14301 -2.1135 O 0.40352 0.69433 -3.85575 C 1.0477 1.77889 -4.18431 O 1.77691 2.40477 -3.41193 C 0.83019 2.22225 -5.60499 C -0.00275 1.50334 -6.46944 C 1.48053 3.37541 -6.05395 C -0.16936 1.95509 -7.77201 H -0.50841 0.61021 -6.1274 C 1.29889 3.80868 -7.36398 H 2.1221 3.91947 -5.37242 C 0.47141 3.10114 -8.23503 H 1.80277 4.70254 -7.7149 H 0.32632 3.43376 -9.2558 Cl -1.21762 1.05364 -8.86561 C 0.80487 0.51389 0.32886 H 1.36356 1.39695 0.63115 C 1.43553 -0.50316 -0.36187 Te 0.00159 -2.09643 -0.73043 O 0.38792 -3.36532 0.56527 C -2.70957 -0.93765 0.54083 C -3.41735 -1.89614 -0.20978 C -3.41214 -0.23081 1.54113 C -4.77178 -2.12128 0.00779 H -2.9168 -2.46009 -0.98991 C -4.76212 -0.46361 1.76137 H -2.89059 0.48781 2.16243 C -5.45036 -1.40705 0.99398 H -5.2953 -2.85835 -0.59109 H -5.28005 0.08539 2.5405 H -6.50516 -1.58793 1.17014 C 2.88088 -0.71596 -0.4802

C 3.43256 -1.36766 -1.59583 C 3.74141 -0.29162 0.54672 C 4.80453 -1.5699 -1.69033 H 2.78635 -1.68544 -2.40699 C 5.11507 -0.49494 0.44733 H 3.33299 0.17866 1.43429 C 5.65121 -1.13406 -0.66958 H 5.21473 -2.06713 -2.56277 H 5.76488 -0.16458 1.25078 H 6.72126 -1.29643 -0.74318 Total Energy: -1655.772426 Hartrees

  73

TSA-C Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C 1.02434 0.60799 -0.12636 C 0.14345 1.47124 -0.65173 H 1.98687 0.95611 0.23995 C -1.39818 -2.44254 0.13351 C -2.1058 -2.25316 1.32907 C -1.489 -3.66414 -0.54678 C -2.8838 -3.28559 1.84393 H -2.04884 -1.30402 1.85023 C -2.26813 -4.69211 -0.02414 H -0.9398 -3.80714 -1.47067 C -2.96684 -4.50481 1.16965 H -3.42655 -3.13805 2.77124 H -2.33026 -5.63989 -0.54807 H -3.57528 -5.30711 1.57333 C 0.34086 2.90748 -0.87726 C -0.6883 3.82623 -0.6165 C 1.57914 3.38593 -1.33687 C -0.47496 5.19006 -0.7909 H -1.65045 3.47548 -0.2576 C 1.78577 4.75068 -1.51352 H 2.37017 2.68365 -1.57644 C 0.76114 5.65662 -1.23872 H -1.27655 5.88922 -0.5782 H 2.74447 5.10591 -1.87667 H 0.92253 6.72002 -1.38069 O -2.96863 1.36283 -5.49391 C -2.32399 2.41249 -5.54664 O -1.5674 2.84812 -4.57884 C -2.34863 3.30442 -6.75612 C -1.60874 4.49142 -6.79428 C -3.12962 2.92551 -7.85183 C -1.66512 5.28006 -7.93578 H -1.00354 4.78872 -5.94829 C -3.17086 3.73314 -8.98445 H -3.6965 2.00435 -7.80477 C -2.43792 4.91804 -9.03591

Cl -0.7351 6.77601 -7.99201 H -3.77631 3.44292 -9.83603 H -2.46633 5.55011 -9.91532 O -1.69491 1.62689 -3.25066 H -2.31611 1.09633 -3.81466 Te -1.66594 0.47255 -1.25618 O -2.97188 0.97294 -0.05418 C 0.72666 -0.83489 0.00814 H 1.2895 -1.40608 0.73845 C -0.58094 -1.35257 -0.42276 O 0.51448 -1.59879 -1.24762 Total Energy: -1730.993131 Hartrees

  74

TSA-B Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.11743 -0.70417 -0.35548 C -0.46067 0.42999 -0.78225 H -0.89589 1.41307 -0.63513 O -1.21563 0.04981 -2.5876 H -2.13615 0.35782 -2.39446 O -1.60926 0.19953 -4.3574 C -2.813 0.68787 -4.43813 O -3.51476 0.94813 -3.45655 C -3.30044 0.91413 -5.84276 C -2.4714 0.67025 -6.9432 C -4.60594 1.37561 -6.03533 C -2.96713 0.8957 -8.22067 H -1.46043 0.31309 -6.79909 C -5.08161 1.59256 -7.32514 H -5.2342 1.56023 -5.17307 C -4.26505 1.35416 -8.42991 H -6.09409 1.94995 -7.47756 H -4.62985 1.522 -9.43617 Cl -1.92644 0.5936 -9.61086 C 1.00865 0.38913 -1.02252 H 1.55614 1.31302 -0.86539 Te 0.16129 -2.47214 -0.53998 O 0.33912 -3.01199 1.22259 C -2.44585 -0.78023 0.22568 C -3.20609 -1.9639 0.16102 C -2.99987 0.33687 0.88718 C -4.47879 -2.02323 0.71347 H -2.81403 -2.8382 -0.34738 C -4.26841 0.26989 1.44566 H -2.42434 1.25 0.98435 C -5.01438 -0.90748 1.35718 H -5.05249 -2.94056 0.64332 H -4.67538 1.13475 1.95795 H -6.00562 -0.95652 1.79459 C 3.083 -1.10103 -0.33168 C 4.17324 -1.08603 -1.20938

C 3.29341 -1.31329 1.03786 C 5.46471 -1.26497 -0.71805 H 4.00575 -0.92578 -2.26832 C 4.58713 -1.49059 1.52105 H 2.44815 -1.35115 1.71595 C 5.6744 -1.46657 0.6462 H 6.30705 -1.2475 -1.40172 H 4.74606 -1.65084 2.58217 H 6.68096 -1.60549 1.02672 C 1.71071 -0.90141 -0.8489 O 1.51258 -0.38042 -2.146 Total Energy: -1730.982149 Hartrees

  75

TSB-D Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.42311 -2.32609 0.07881 C -2.11494 -2.00165 1.25476 C -1.62386 -3.57266 -0.53061 C -2.98512 -2.92736 1.82235 H -1.97665 -1.03065 1.7162 C -2.49358 -4.49296 0.04533 H -1.08874 -3.8193 -1.44082 C -3.17594 -4.17194 1.22037 H -3.51582 -2.67657 2.73427 H -2.64009 -5.46067 -0.42221 H -3.85594 -4.89045 1.66547 C 0.44681 2.93108 -0.7646 C -0.22028 3.4767 0.34006 C 1.1226 3.77121 -1.65594 C -0.19501 4.85182 0.55577 H -0.7625 2.82976 1.02071 C 1.14569 5.14591 -1.43204 H 1.62857 3.34672 -2.51523 C 0.48791 5.68832 -0.32819 H -0.71077 5.27022 1.4135 H 1.67373 5.79374 -2.12371 H 0.5051 6.75972 -0.15798 O -2.8818 1.29319 -5.68934 C -2.23483 2.33965 -5.79043 O -1.4566 2.80366 -4.85792 C -2.2901 3.19017 -7.02988 C -1.54506 4.37026 -7.12926 C -3.10404 2.78007 -8.08968 C -1.62874 5.12046 -8.29473 H -0.91509 4.69166 -6.31062 C -3.1724 3.54938 -9.24752 H -3.67458 1.86479 -7.99561 C -2.43441 4.72695 -9.35985 Cl -0.6918 6.60743 -8.42737 H -3.80338 3.23474 -10.07146 H -2.48412 5.32921 -10.25903

O -1.57379 1.60311 -3.47221 H -2.20455 1.07213 -4.02698 Te -1.50145 0.50444 -1.48068 O -2.68628 1.10556 -0.20613 C 0.84569 -0.9362 -0.14821 H 1.33941 -1.47545 0.65404 C -0.51206 -1.35228 -0.53939 O 0.56894 -1.75827 -1.31792 C 1.32541 0.46689 -0.40998 H 2.14401 0.81653 0.21124 O 1.42479 0.86265 -1.79237 C 0.4149 1.46914 -1.00375 Total Energy: -1806.206978 Hartrees

  76

TSC-D Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C -1.20511 -0.73384 -0.29062 C -0.54541 0.3841 -0.76685 H -0.96629 1.37024 -0.60525 O -1.22026 0.05422 -2.51889 H -2.17852 0.26888 -2.37534 O -1.53401 0.30862 -4.31441 C -2.77483 0.68208 -4.41603 O -3.53498 0.80471 -3.44962 C -3.2311 0.95887 -5.82198 C -2.34191 0.87305 -6.8988 C -4.56785 1.30519 -6.03949 C -2.80983 1.13976 -8.17873 H -1.30739 0.60247 -6.73491 C -5.01452 1.5656 -7.33165 H -5.24294 1.36633 -5.19525 C -4.13807 1.48541 -8.41309 H -6.05124 1.83305 -7.50412 H -4.4806 1.68742 -9.42088 Cl -1.69401 1.03761 -9.53915 C 0.93639 0.36495 -1.01696 H 1.45267 1.31142 -0.90203 O 0.28971 -3.03282 1.37135 C -2.52689 -0.83433 0.28073 C -3.19931 -2.07282 0.32906 C -3.17 0.30738 0.8101 C -4.47368 -2.16393 0.87027 H -2.73757 -2.96388 -0.08305 C -4.43987 0.20667 1.35575 H -2.66533 1.26628 0.81229 C -5.09701 -1.02674 1.38516 H -4.98071 -3.12168 0.89064 H -4.91944 1.08832 1.76592 H -6.0907 -1.10022 1.81319 C 3.09665 -1.07942 -0.38573 C 4.07444 -1.51669 -1.28748 C 3.42726 -0.85122 0.95606

C 5.37987 -1.7142 -0.84794 H 3.81264 -1.69011 -2.32525 C 4.73494 -1.05227 1.38745 H 2.67155 -0.51435 1.65766 C 5.71071 -1.48451 0.48815 H 6.13832 -2.04746 -1.54775 H 4.99248 -0.87078 2.42508 H 6.72863 -1.6411 0.8287 C 1.719 -0.87255 -0.86306 O 1.43266 -0.42167 -2.14322 Te 0.1606 -2.41482 -0.3366 O -0.26282 -3.66132 -1.59521 Total Energy: -1806.148817 Hartrees

  77

Figure S3. IRC path leading from TSPT-PTO to the connected reactant and product geometries.

These structures resemble the expected reactants (PT + MCPBA) and products (PT-O + CBA).

  78

Figure S4. IRC path leading from TSPTO-PTO2 to the connected reactant and product geometries.

These structures resemble the expected reactants (PT-O + MCPBA) and products (PT-O2 +

CBA).

  79

Figure S5. IRC path leading from TSPTO2-C to the connected reactant and product geometries.

The structure obtained in the reverse direction resembles the expected reactants (PT-O2 +

MCPBA), while the forward structure resembles a ring-opened product and CBA. Optimization

from this structure leads to the diphenylfuran (IntC’ + TeO2 + CBA).

  80

Figure S6. IRC path leading from TSC’-(Z)-ED to the connected reactant and product geometries.

These structures resemble the expected reactants (IntC’ + MCPBA) and products ((Z)-ED +

CBA).

  81

Figure S7. IRC path leading from TSPTO-A to the connected reactant and product geometries.

These structures resemble the expected reactants (PT-O + MCPBA) and products (IntA +

CBA).

  82

Figure S8. IRC path leading from TSA-C to the connected reactant and product geometries. The

structure obtained in the reverse direction resembles the expected reactants (IntA + MCPBA),

while the forward structure resembles a ring-opened product and CBA. Optimization from this

structure leads to the diphenylfuran (IntC’ + TeO2 + CBA).

  83

Figure S9. IRC path leading from TSA-B to the connected reactant and product geometries.

These structures resemble the expected reactants (IntA + MCPBA) and products (IntB + CBA).

  84

Figure S10. IRC path leading from TSB-D to the connected reactant and product geometries.

These structures resemble the expected reactants (IntB + MCPBA) and products (IntD + CBA).

  85

Figure S11. Relative energy diagram for Paths A (green), B’ (blue) and C’ (red).