Supplementary Materials for. Kinetic and Computational Studies on Pd(I) Dimer- Mediated Halogen Exchange of Aryl Iodides

Supplementary Materials for Kinetic and Computational Studies on Pd(I) Dimer- Mediated Halogen Exchange of Aryl Iodides Indrek Kalvet, a Karl J. Bonney, a and Franziska Schoenebeck a * a Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany Email: franziska.schoenebeck@rwth-aachen.de Contents: ps2-4 ps6-28 ps29-33 ps34 Kinetic data; Computational data; NMR spectra of used compounds; References. ps1

Kinetic Data Scheme S1. Halogen exchange between [(PtBu3P)PdBr]2 (1) and 5. Aryl Iodide 7 Study 7,0 0,12 [ArBr] mm 6,0 5,0 4,0 3,0 2,0 1,0 0,0 0 20 40 60 t (min) 41 mm [ArI] 82 mm [ArI] 123 mm [ArI] 158 mm [ArI] 200 mm [ArI] d[arbr]/dt (mm/min) 0,10 0,08 0,06 R² = 0,9976 0,04 0,02 0,00 0,00 0,10 0,20 [ArI](M) Figure S1. Rate of formation of 6 with different initial concentrations of 5 (quantified by integration of the proton at 6.68 ppm against the CH2 resonance of the internal standard at 3.82 ppm). Table S1. R 2 values, demonstrating the fit of the data to the applied linear trendlines in Figure S1, and values for the gradient of the trendline for each [ArI]0. [ArI]0(mM) R 2 d[arbr]/dt (mm/min) 41 0.990 0.019 82 0.995 0.037 123 0.987 0.058 158 0.995 0.075 200 0.988 0.098 ps2

[(PtBu3P)PdBr]2 (1) Study 3,0 [ArBr] (mm) 2,5 2,0 1,5 1,0 0,5 0,0 0 10 20 30 40 50 t (min) [1] (mm) 11.3 9.4 7.6 5.7 3.8 Figure S2. Rate of formation of 6 with different initial concentrations of 1. d[arbr]/dt (mm/min) 0,08 0,07 0,06 0,05 0,04 0,03 0,02 0,01 0,00 R² = 0,988 2 5 8 11 [1](mM) Table S2. R 2 values, demonstrating the fit of the data to the applied linear trendlines in Figure S2, and values for the gradient of the trendline for each [1]0. [1]0(mM) R 2 d[arbr]/dt (mm/min) 3.8 0.977 0.022 5.7 0.998 0.036 7.6 0.999 0.048 9.4 0.995 0.054 11.3 0.999 0.066 ps3

Activation Barrier Study A [ArBr] mm 3,5 3,0 2,5 2,0 1,5 1,0 0,5 0,0 0 15 30 45 Figure S3. A - Formation of 6 at different temperatures. B - logarithm of [1] vs time at different temperatures. t (min) t( o C) 65 60 55 50 45 B ln([1]) -4,55-4,65-4,75-4,85-4,95 t (min) 0 20 40 60 t( o C) 65 60 55 50 45 rate*10 6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 40 45 50 55 60 65 70 t ( o C) Figure S4. Rate of consumption of 1 at different temperatures. Table S3. R 2 values, demonstrating the fit of the data to the applied linear trendlines in Figure S3-B, and absolute values for the gradient of the trendline for each temperature. t ( o C) R 2 gradient 45 0.993 0.239 50 0.997 0.382 55 0.997 0.598 60 0.992 0.784 65 0.997 1.244 ps4

Computational data Computational Methods. All calculations were performed with the Gaussian 09 program package.1 Structural optimizations and frequency calculations were performed with B3LYP and ωb97xd functionals along with 6-31G(d) basis set on lighter atoms and the ECP LanL2DZ on Pd and I atoms. Single point energy calculations were performed with alternative DFT methods and 6-311++G(d,p) basis set on lighter and Stuttgart-Dresden ECP on Pd and I atoms (BS1) or def2-tzvp on all atoms (BS2). Benzene solvation was taken into account using the CPCM solvation model. Frequency analysis was used to confirm whether the structure is a minima (NImag = 0) or a transition state (NImag = 1). Intrinsic reaction coordinate (IRC) analysis was used to confirm that the obtained transition states connect the correct minima. D3-corrections have been calculated using the Becke-Johnson damping function. 2 All energies were corrected to 1M standard state.3 Data from ωb97xd optimized structures Figure S5. Free energy pathway of the halogen exchange reaction between Br-dimer 1 and 1- iodo-2-methoxynaphthalene 5, calculated at CPCM (benzene) M06L/def2TZVP //ωb97xd/6-31g(d) [with LANL2DZ for Pd,I]. Values are reported in kcal/mol. Table S4. Comparison of experimentally obtained activation free energy barrier with calculated activation free energies. Different solvation corrected (CPCM=benzene) single point energies were calculated with 6-311++G(d,p) basis set and SDD ECP (BS1) or def2tzvp (BS2) on //ωb97xd/6-31g(d)[with LANL2DZ for Pd,I] optimized geometries. All values are reported in kcal/mol and are relative to the starting materials 1 and 5. Method TS-1 (Ox. Add.) G TS-2 (Red. Elim.) Experiment 24.9± 3.3 M06L/BS1 14.6 17.4 M06L/BS2 18.3 23.4 M06-2X/BS1 18.3 24.2 M06-2X/BS2 22.1 27.0 ωb97xd/bs1 18.9 22.5 ωb97xd/bs2 22.4 27.5 B3LYP/BS1 46.7 50.3 B3LYP/BS2 48.7 53.2 BP86/BS1 38.7 41.6 BP86/BS2 40.9 44.8 B3LYP-D3/BS1 12.2 16.3 B3LYP-D3/BS2 14.1 19.2 BP86-D3/BS1 0.3 3.7 BP86-D3/BS2 2.5 6.9 ps5

XYZ and thermal data 1 Pd 1.327961000-0.014873000-0.133672000 Br -0.029792000-2.219065000-0.079232000 P 3.691391000-0.005482000 0.001230000 C 4.496036000 1.125306000-1.364669000 C 4.136529000 0.701035000 1.759752000 C 4.419967000-1.804830000-0.166486000 Br 0.029965000 2.218937000-0.079234000 Pd -1.328049000 0.014922000-0.133642000 P -3.691431000 0.005610000 0.001245000 C -4.136658000-0.701613000 1.759455000 C -4.420129000 1.804950000-0.165880000 C -4.495805000-1.124809000-1.365110000 C 3.140062000 0.098782000 2.781317000 H 3.325697000 0.559775000 3.760934000 H 2.104794000 0.312802000 2.495982000 H 3.239501000-0.979905000 2.902430000 C 5.577732000 0.432145000 2.239364000 H 6.332521000 0.833566000 1.558095000 H 5.722153000 0.922102000 3.211862000 H 5.780751000-0.631707000 2.385515000 C 3.888821000 2.226097000 1.783017000 H 4.624097000 2.787637000 1.202176000 H 2.885387000 2.482812000 1.429886000 H 3.970804000 2.569885000 2.822426000 C 3.630393000 2.396486000-1.533366000 H 3.606483000 3.028702000-0.646030000 H 4.053878000 2.994199000-2.351865000 H 2.597839000 2.148037000-1.792031000 C 5.954368000 1.546178000-1.086468000 H 6.323875000 2.124498000-1.944227000 H 6.043003000 2.189041000-0.207124000 H 6.625563000 0.694140000-0.954932000 C 4.443859000 0.402209000-2.728931000 H 3.436229000 0.042603000-2.961126000 H 4.724961000 1.120598000-3.509884000 H 5.141667000-0.435093000-2.797863000 C 4.049575000-2.624493000 1.090016000 H 4.313295000-3.673882000 0.904936000 H 4.595258000-2.310427000 1.982686000 H 2.975508000-2.588534000 1.296761000 C 3.724279000-2.518226000-1.351616000 H 3.950973000-2.074375000-2.320847000 H 4.076303000-3.558251000-1.379258000 H 2.638615000-2.534957000-1.227323000 C 5.948134000-1.877556000-0.369188000 H 6.250976000-2.933338000-0.380100000 H 6.264511000-1.446448000-1.322387000 H 6.508299000-1.386708000 0.430374000 C -3.888874000-2.226665000 1.782281000 H -2.885413000-2.483243000 1.429118000 H -3.970868000-2.570748000 2.821594000 H -4.624107000-2.788075000 1.201280000 C -5.577919000-0.433003000 2.239044000 H -5.722356000-0.923182000 3.211430000 H -5.781074000 0.630793000 2.385405000 H -6.332596000-0.834369000 1.557631000 C -3.140295000-0.099647000 2.781285000 H -2.105010000-0.313468000 2.495888000 H -3.239761000 0.978984000 2.902802000 H -3.325932000-0.561038000 3.760718000 C -3.630044000-2.395868000-1.534104000 H -3.606520000-3.028554000-0.647074000 H -4.053155000-2.993155000-2.353105000 H -2.597376000-2.147290000-1.792185000 C -4.443512000-0.401231000-2.729116000 ps6

H -3.435922000-0.041322000-2.960996000 H -4.724337000-1.119389000-3.510379000 H -5.141492000 0.435937000-2.797864000 C -5.954140000-1.545919000-1.087276000 H -6.323420000-2.124085000-1.945237000 H -6.042846000-2.188987000-0.208104000 H -6.625473000-0.693991000-0.955670000 C -5.948276000 1.877636000-0.368826000 H -6.251206000 2.933399000-0.379288000 H -6.264402000 1.447005000-1.322325000 H -6.508591000 1.386349000 0.430348000 C -3.724363000 2.518930000-1.350632000 H -3.951046000 2.075576000-2.320096000 H -4.076374000 3.558969000-1.377751000 H -2.638713000 2.535559000-1.226303000 C -4.049928000 2.624161000 1.090988000 H -4.313941000 3.673552000 0.906383000 H -4.595481000 2.309557000 1.983554000 H -2.975847000 2.588387000 1.297704000 B3LYP optimization 0.749307 Thermal correction to Energy= 0.795126 Thermal correction to Enthalpy= 0.796070 Thermal correction to Gibbs Free Energy= 0.670961 Sum of electronic and zero-point Energies= -7025.485688 Sum of electronic and thermal Energies= -7025.439869 Sum of electronic and thermal Enthalpies= -7025.438924 Sum of electronic and thermal Free Energies= -7025.564033 CPCM (Benzene) M06L/def2-TZVP E = -7034.3509526 CPCM (Benzene) M062X/def2TZVP E = -7033.8386137 CPCM (Benzene) BP86/def2TZVP E = -7035.2876205 CPCM (Benzene) B3LYP/def2TZVP E = -7034.652076 CPCM (Benzene) wb97xd/def2tzvp E = -7034.4265525 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd) E = -7034.0995775 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd) E = -7033.6459682 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd) E = -7035.0678077 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd) E = -7034.19472868 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd) E = -7034.42305 BP86-D3 correction = -0.2377514 B3LYP-D3 correction = -0.2397529 ωb97xd optimization 0.759172 (Hartree/Particle) Thermal correction to Energy= 0.803249 Thermal correction to Enthalpy= 0.804193 Thermal correction to Gibbs Free Energy= 0.683953 Sum of electronic and zero-point Energies= -7025.269849 Sum of electronic and thermal Energies= -7025.225771 Sum of electronic and thermal Enthalpies= -7025.224827 Sum of electronic and thermal Free Energies= -7025.345067 CPCM (Benzene) M06L/def2TZVP E = -7034.35603177 CPCM (Benzene) M062X/def2TZVP E = -7033.84357583 CPCM (Benzene) wb97xd/def2tzvp E = -7034.43319037 CPCM (Benzene) BP86/def2TZVP E = -7035.28730296 CPCM (Benzene) B3LYP/def2TZVP E = -7034.65118004 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd) E = -7034.10302331 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd) E = -7033.64903136 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd) E = -7034.19961225 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd) E = -7035.06565909 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd) E = -7034.42031581 BP86-D3 correction = -0.24269521 B3LYP-D3 correction = -0.2449401 ps7

Ox. Add. TS-1 C -5.602398000-2.056099000-0.402362000 C -3.482578000-1.985378000 0.843949000 C -2.822104000-1.632955000-0.380047000 C -3.534606000-1.601927000-1.588430000 C -4.939569000-1.781390000-1.577732000 C -4.907347000-2.177278000 0.825756000 Pd -1.296398000-0.048146000-0.226557000 Pd 1.549813000-0.115834000 0.003744000 Br 1.281777000 0.292200000-2.455500000 H -6.679378000-2.203654000-0.413316000 H -1.710623000 2.719900000 3.950394000 C -1.360344000 2.761305000 2.910339000 C -2.590975000 2.602592000 1.987751000 H -0.638596000 1.949558000 2.777332000 H -0.850151000 3.719265000 2.785990000 P -2.007854000 2.330481000 0.145429000 C -3.536916000 3.798975000 2.224090000 C -3.291052000 1.309596000 2.457971000 C -0.675156000 3.698818000-0.258010000 C -3.529039000 2.636591000-1.035423000 H -4.501526000 3.680699000 1.724180000 H -3.743652000 3.869213000 3.300811000 H -3.106733000 4.754189000 1.914551000 H -4.194163000 1.066419000 1.896994000 H -2.614066000 0.455787000 2.394036000 H -3.580548000 1.432058000 3.510529000 C -1.017410000 5.114336000 0.255558000 C 0.677213000 3.273600000 0.355685000 C -0.437658000 3.778406000-1.782821000 C -3.178127000 2.053415000-2.425820000 C -4.745860000 1.839358000-0.516792000 C -3.969035000 4.103884000-1.221214000 H -1.968807000 5.492184000-0.124494000 H -1.038791000 5.171578000 1.345986000 H -0.233390000 5.804036000-0.085938000 H 1.011103000 2.313126000-0.049219000 H 1.428704000 4.029250000 0.087397000 H 0.663658000 3.191469000 1.441587000 H 0.434784000 4.422478000-1.956396000 H -0.208040000 2.800763000-2.215527000 H -1.274273000 4.228162000-2.322241000 H -2.404552000 2.620420000-2.943538000 H -2.838918000 1.016983000-2.360379000 H -4.080459000 2.083954000-3.053085000 H -5.175982000 2.264498000 0.392632000 H -5.529791000 1.866621000-1.285406000 H -4.506358000 0.790278000-0.332024000 H -4.862522000 4.119972000-1.860752000 H -4.236002000 4.593859000-0.282018000 H -3.210985000 4.710333000-1.721605000 P 4.032255000-0.106240000 0.166042000 C 4.696948000-0.300339000 2.006842000 C 4.588751000-1.684576000-0.851675000 C 4.913089000 1.472930000-0.591187000 C 6.229599000-0.156365000 2.160799000 C 4.050027000 0.755675000 2.935384000 C 4.285062000-1.688486000 2.547049000 C 3.560295000-2.805689000-0.573399000 C 4.530392000-1.406274000-2.369377000 C 6.003531000-2.208059000-0.525020000 C 4.805892000 2.656387000 0.396104000 C 6.406441000 1.250265000-0.925267000 C 4.203866000 1.932108000-1.881192000 H 6.806507000-0.838702000 1.535189000 H 6.574953000 0.862927000 1.972719000 H 6.479221000-0.385142000 3.205421000 H 2.962142000 0.728304000 2.896081000 ps8

H 4.347701000 0.516772000 3.965223000 H 4.390067000 1.770288000 2.732643000 H 4.545261000-1.727663000 3.612903000 H 3.208208000-1.850908000 2.469610000 H 4.813611000-2.510233000 2.059405000 H 3.476356000-3.071474000 0.481037000 H 2.567045000-2.521236000-0.930338000 H 3.871765000-3.704741000-1.122267000 H 5.323190000-0.736101000-2.709660000 H 4.673290000-2.362499000-2.890022000 H 3.564395000-1.002356000-2.678525000 H 6.209926000-3.057128000-1.190093000 H 6.783812000-1.463927000-0.702423000 H 6.098988000-2.575190000 0.498336000 H 3.784595000 2.801756000 0.760721000 H 5.474908000 2.557727000 1.252646000 H 5.098721000 3.570408000-0.136340000 H 6.548383000 0.546091000-1.747680000 H 6.827184000 2.210889000-1.251871000 H 6.998996000 0.909649000-0.075426000 H 4.182286000 1.174483000-2.662316000 H 3.173452000 2.234752000-1.694256000 H 4.752520000 2.800790000-2.270858000 C -5.583113000-2.509702000 2.031395000 C -2.800248000-2.169301000 2.077077000 H -6.662666000-2.638992000 1.999476000 H -1.726074000-2.020451000 2.110909000 C -3.486012000-2.509803000 3.223264000 C -4.891296000-2.676533000 3.208306000 H -5.417280000-2.938043000 4.122311000 H -2.937523000-2.644315000 4.151549000 H -5.498185000-1.708376000-2.503879000 O -2.832511000-1.398613000-2.732683000 C -3.491265000-1.503849000-3.987174000 H -4.235191000-0.708251000-4.120831000 H -2.706036000-1.391705000-4.735718000 H -3.973989000-2.482039000-4.105859000 I -0.656412000-2.647484000-0.677141000 Br 0.838862000-0.541605000 2.375120000 B3LYP optimization 0.920658 (Hartree/Particle) Thermal correction to Energy= 0.978717 Thermal correction to Enthalpy= 0.979661 Thermal correction to Gibbs Free Energy= 0.829522 Sum of electronic and zero-point Energies= -7536.454302 Sum of electronic and thermal Energies= -7536.396243 Sum of electronic and thermal Enthalpies= -7536.395299 Sum of electronic and thermal Free Energies= -7536.545438 CPCM (Benzene) M06L/def2TZVP E = -7832.1420751 CPCM (Benzene) M062X/def2TZVP E = -7831.2410528 CPCM (Benzene) BP86/def2TZVP E = -7833.0805489 CPCM (Benzene) B3LYP/def2TZVP E = -7832.4021101 CPCM (Benzene) wb97xd/def2tzvp E = -7832.0119488 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd, I) E = -7545.3717873 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd, I) E = -7544.7325954 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd, I) E = -7546.4181998 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd, I) E = -7545.3654468 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd, I) E = -7545.7299314 BP86-D3 correction = -0.3407093 B3LYP-D3 correction = -0.3391628 ωb97xd optimization 0.933734 (Hartree/Particle) Thermal correction to Energy= 0.989414 Thermal correction to Enthalpy= 0.990358 Thermal correction to Gibbs Free Energy= 0.846574 Sum of electronic and zero-point Energies= -7536.113556 Sum of electronic and thermal Energies= -7536.057876 Sum of electronic and thermal Enthalpies= -7536.056932 Sum of electronic and thermal Free Energies= -7536.200716 CPCM (Benzene) M06L/def2TZVP E = -7832.15182559 CPCM (Benzene) M062X/def2TZVP E = -7831.25193871 ps9

CPCM (Benzene) wb97xd/def2tzvp E = -7832.02460143 CPCM (Benzene) BP86/def2TZVP E = -7833.07741576 CPCM (Benzene) B3LYP/def2TZVP E = -7832.3971053 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd, I) E = -7545.37906955 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd, I) E = -7544.7401722 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd, I) E = -7545.37567935 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd, I) E = -7546.41215877 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd, I) E = -7545.72201671 BP86-D3 correction = -0.35288019 B3LYP-D3 correction = -0.35157653 C -4.841588000-3.698234000-0.426422000 C -3.661621000-2.094960000 1.015228000 C -3.124592000-1.474647000-0.148674000 C -3.419100000-1.994062000-1.401826000 C -4.285794000-3.108346000-1.539994000 C -4.547508000-3.222230000 0.873881000 Pd -1.756503000 0.005352000-0.015306000 Pd 2.360629000-0.663335000-0.004815000 Br 0.665076000 1.275144000 0.303606000 H -5.507388000-4.550368000-0.539303000 H -6.658227000 0.881695000 1.588876000 C -5.615494000 1.221855000 1.540415000 C -5.299534000 1.576187000 0.069105000 H -4.993413000 0.402175000 1.908674000 H -5.524664000 2.067327000 2.224363000 P -3.373570000 1.908565000-0.142138000 C -6.187568000 2.766582000-0.363786000 C -5.759711000 0.351178000-0.757496000 C -2.880713000 3.192543000 1.259600000 C -3.107267000 2.750533000-1.882030000 H -6.194961000 2.895770000-1.449002000 H -7.220314000 2.544605000-0.063906000 H -5.915209000 3.718001000 0.091878000 H -5.449683000 0.376915000-1.800674000 H -5.408027000-0.581151000-0.323056000 H -6.857768000 0.332989000-0.739716000 C -3.930640000 4.281421000 1.574329000 C -2.595738000 2.374937000 2.542385000 C -1.574499000 3.941383000 0.915729000 C -1.602602000 2.676196000-2.225541000 C -3.836799000 1.936385000-2.973708000 C -3.570815000 4.219806000-1.984258000 H -4.153670000 4.910023000 0.707904000 H -4.868615000 3.887698000 1.966560000 H -3.512940000 4.938500000 2.348737000 H -1.767259000 1.677121000 2.389007000 H -2.307146000 3.067958000 3.344086000 H -3.459420000 1.807503000 2.892580000 H -1.282939000 4.527918000 1.797036000 H -0.749229000 3.267934000 0.692279000 H -1.689947000 4.643697000 0.088236000 H -0.967955000 3.220063000-1.525833000 H -1.252417000 1.640505000-2.257555000 H -1.453938000 3.116123000-3.221090000 H -4.921606000 2.063420000-2.943050000 H -3.499736000 2.303449000-3.952282000 H -3.597306000 0.871142000-2.916465000 H -3.405390000 4.559792000-3.015489000 H -4.632480000 4.349433000-1.767526000 H -3.005996000 4.890628000-1.334066000 P 4.509460000 0.613374000 0.222411000 C 6.158541000-0.457586000 0.132930000 C 4.525710000 1.870399000-1.274241000 C 4.588144000 1.611636000 1.906666000 C 7.440555000 0.315293000 0.520628000 ps10

C 6.060620000-1.680577000 1.077943000 C 6.352389000-0.999012000-1.302624000 C 3.992214000 1.109928000-2.512183000 C 3.552792000 3.044920000-1.026348000 C 5.901997000 2.485931000-1.608896000 C 4.946858000 0.657238000 3.067851000 C 5.596942000 2.782857000 1.896199000 C 3.203544000 2.188697000 2.262411000 H 7.604975000 1.219333000-0.067425000 H 7.470795000 0.577591000 1.580114000 H 8.294056000-0.350499000 0.336639000 H 5.173063000-2.281567000 0.886277000 H 6.936602000-2.315132000 0.888884000 H 6.085502000-1.407638000 2.132068000 H 7.199538000-1.696911000-1.284870000 H 5.480739000-1.552427000-1.653174000 H 6.599721000-0.215715000-2.021609000 H 4.596955000 0.243718000-2.783698000 H 2.966594000 0.763311000-2.353427000 H 3.989003000 1.798341000-3.367934000 H 3.900579000 3.733322000-0.251884000 H 3.482202000 3.622301000-1.957860000 H 2.547047000 2.707240000-0.774025000 H 5.761414000 3.200992000-2.430474000 H 6.330939000 3.040036000-0.769939000 H 6.634425000 1.752940000-1.950230000 H 4.325531000-0.243944000 3.068247000 H 5.996968000 0.361253000 3.072209000 H 4.758842000 1.185896000 4.011150000 H 5.294085000 3.585074000 1.219607000 H 5.627666000 3.212828000 2.906401000 H 6.614017000 2.485840000 1.640242000 H 2.793900000 2.849032000 1.499854000 H 2.473437000 1.399304000 2.447501000 H 3.311594000 2.772888000 3.186352000 C -5.087203000-3.836381000 2.037631000 C -3.347693000-1.662525000 2.338411000 H -5.755948000-4.685239000 1.911105000 H -2.656394000-0.833582000 2.456965000 C -3.882799000-2.285268000 3.443828000 C -4.768322000-3.382106000 3.295735000 H -5.184172000-3.865241000 4.175747000 H -3.618459000-1.938455000 4.439500000 H -4.519506000-3.498853000-2.524742000 O -2.864816000-1.361614000-2.490784000 C -2.840497000-2.046305000-3.735477000 H -3.842844000-2.134819000-4.176237000 H -2.215140000-1.441252000-4.394757000 H -2.398364000-3.044773000-3.633788000 I 0.011509000-2.113401000-0.046377000 Br 3.345364000-2.817336000-0.794825000 B3LYP optimization 0.921709 (Hartree/Particle) Thermal correction to Energy= 0.980286 Thermal correction to Enthalpy= 0.981230 Thermal correction to Gibbs Free Energy= 0.827437 Sum of electronic and zero-point Energies= -7536.498289 Sum of electronic and thermal Energies= -7536.439712 Sum of electronic and thermal Enthalpies= -7536.438768 Sum of electronic and thermal Free Energies= -7536.592561 CPCM (Benzene) M06L/def2-TZVP E = -7832.162827 ωb97xd optimization 0.935279 (Hartree/Particle) Thermal correction to Energy= 0.991272 Thermal correction to Enthalpy= 0.992217 Thermal correction to Gibbs Free Energy= 0.848109 Sum of electronic and zero-point Energies= -7536.154947 Sum of electronic and thermal Energies= -7536.098954 Sum of electronic and thermal Enthalpies= -7536.098010 Sum of electronic and thermal Free Energies= -7536.242117 CPCM (Benzene) M06L/def2-TZVP E = -7832.17173759 ps11

C 4.375552000-4.065785000-0.102858000 C 3.431513000-2.146014000-1.313296000 C 3.003347000-1.600330000-0.070011000 C 3.221746000-2.307260000 1.103638000 C 3.918887000-3.542420000 1.086104000 C 4.144573000-3.397569000-1.329622000 Pd 1.814072000 0.025234000 0.005643000 Pd -2.195930000-0.440757000-0.014538000 Br -0.467695000 1.530098000-0.088736000 H 4.911616000-5.011709000-0.109016000 H 6.719075000 0.569157000-1.670699000 C 5.718949000 1.002731000-1.539643000 C 5.480707000 1.195799000-0.023896000 H 5.006256000 0.303053000-1.983223000 H 5.699736000 1.933682000-2.108995000 P 3.611961000 1.704250000 0.302819000 C 6.504443000 2.221842000 0.516903000 C 5.824055000-0.166332000 0.624563000 C 3.219023000 3.199545000-0.908536000 C 3.481585000 2.336673000 2.144306000 H 6.548568000 2.217898000 1.608862000 H 7.499732000 1.927971000 0.158089000 H 6.329674000 3.244817000 0.184697000 H 5.563770000-0.236361000 1.679329000 H 5.343742000-0.990046000 0.102835000 H 6.910313000-0.307016000 0.542621000 C 4.373173000 4.200740000-1.134020000 C 2.804100000 2.583452000-2.265869000 C 2.015741000 4.033595000-0.415757000 C 1.986626000 2.379809000 2.533599000 C 4.142715000 1.317774000 3.098983000 C 4.106084000 3.723817000 2.411749000 H 4.689366000 4.688471000-0.207731000 H 5.249655000 3.760214000-1.609717000 H 4.008377000 4.989713000-1.804938000 H 1.914984000 1.955174000-2.156793000 H 2.557745000 3.396958000-2.961448000 H 3.592173000 1.984836000-2.725970000 H 1.762769000 4.752651000-1.206137000 H 1.128524000 3.428769000-0.236644000 H 2.236943000 4.612158000 0.482966000 H 1.398833000 3.072405000 1.931144000 H 1.525537000 1.391504000 2.453515000 H 1.912659000 2.704451000 3.580382000 H 5.233587000 1.324044000 3.037957000 H 3.879143000 1.599141000 4.127234000 H 3.777615000 0.301412000 2.928867000 H 4.006456000 3.942378000 3.483405000 H 5.169574000 3.768248000 2.171003000 H 3.600980000 4.529768000 1.875800000 P -4.306176000 0.815895000-0.370286000 C -5.952611000-0.263729000-0.431989000 C -4.479208000 2.101597000 1.085979000 C -4.213060000 1.776641000-2.078646000 C -7.183452000 0.483862000-0.997027000 C -5.734533000-1.518343000-1.311995000 C -6.323503000-0.747982000 0.988719000 C -4.077021000 1.369986000 2.388333000 C -3.486656000 3.271412000 0.907623000 C -5.883045000 2.722623000 1.257433000 C -4.437304000 0.787412000-3.244407000 C -5.230379000 2.934706000-2.199298000 C -2.808288000 2.369238000-2.309076000 H -7.418552000 1.406368000-0.462834000 H -7.090577000 0.711164000-2.060861000 ps12

H -8.050175000-0.181637000-0.890759000 H -4.862795000-2.097411000-1.009640000 H -6.613534000-2.165959000-1.197099000 H -5.646552000-1.283532000-2.372146000 H -7.147217000-1.466973000 0.892977000 H -5.501259000-1.263933000 1.483829000 H -6.679095000 0.058934000 1.631892000 H -4.723664000 0.524406000 2.626159000 H -3.048918000 0.999605000 2.334439000 H -4.138671000 2.083278000 3.221085000 H -3.753481000 3.932640000 0.079562000 H -3.514672000 3.877144000 1.823082000 H -2.459980000 2.930809000 0.771565000 H -5.833094000 3.446646000 2.081445000 H -6.214207000 3.268145000 0.369973000 H -6.650803000 1.994484000 1.521309000 H -3.798880000-0.097890000-3.160601000 H -5.474834000 0.465868000-3.343878000 H -4.168668000 1.296978000-4.178495000 H -5.005841000 3.755661000-1.514268000 H -5.163036000 3.340857000-3.217431000 H -6.264252000 2.630139000-2.039693000 H -2.492814000 3.067241000-1.535245000 H -2.046908000 1.592128000-2.386338000 H -2.831236000 2.916689000-3.261114000 C 4.579480000-3.936780000-2.571467000 C 3.171659000-1.516324000-2.566738000 H 5.119114000-4.881503000-2.563976000 H 2.603702000-0.590906000-2.567050000 C 3.601320000-2.070357000-3.751968000 C 4.320118000-3.291880000-3.758150000 H 4.654637000-3.718961000-4.699683000 H 3.381167000-1.571497000-4.692336000 H 4.097283000-4.079116000 2.012033000 O 2.771922000-1.742959000 2.274307000 C 2.561372000-2.590785000 3.396253000 H 3.507812000-2.924047000 3.843477000 H 2.016901000-1.988350000 4.125953000 H 1.957228000-3.464447000 3.125005000 Br -0.016598000-1.779719000-0.116172000 I -3.155363000-2.745144000 1.107948000 B3LYP optimization 0.922265 (Hartree/Particle) Thermal correction to Energy= 0.980637 Thermal correction to Enthalpy= 0.981581 Thermal correction to Gibbs Free Energy= 0.829581 Sum of electronic and zero-point Energies= -7536.498169 Sum of electronic and thermal Energies= -7536.439797 Sum of electronic and thermal Enthalpies= -7536.438853 Sum of electronic and thermal Free Energies= -7536.590853 CPCM (Benzene) M06L/def2-TZVP E = -7832.1592537 ωb97xd optimization 0.937382 (Hartree/Particle) Thermal correction to Energy= 0.992510 Thermal correction to Enthalpy= 0.993455 Thermal correction to Gibbs Free Energy= 0.851798 Sum of electronic and zero-point Energies= -7536.152062 Sum of electronic and thermal Energies= -7536.096934 Sum of electronic and thermal Enthalpies= -7536.095990 Sum of electronic and thermal Free Energies= -7536.237646 CPCM (Benzene) M06L/def2-TZVP E = -7832.17165016 ps13

Red. Elim. TS-2 C 5.409823000-2.357417000 1.283929000 C 3.472679000-2.294751000-0.230919000 C 2.741588000-1.628681000 0.805249000 C 3.297389000-1.466444000 2.082775000 C 4.657656000-1.798778000 2.294615000 C 4.848170000-2.633030000 0.012973000 Pd 1.360190000-0.037636000 0.222160000 Pd -1.548721000-0.167648000 0.054862000 Br -1.096215000 0.663325000 2.388180000 H 6.450175000-2.614629000 1.466028000 H 2.580367000 1.793410000-4.233596000 C 2.077465000 2.026467000-3.285685000 C 3.149710000 2.072609000-2.173443000 H 1.335979000 1.241766000-3.107581000 H 1.559169000 2.977621000-3.425721000 P 2.282394000 2.156366000-0.429300000 C 4.136361000 3.216613000-2.487291000 C 3.901738000 0.727160000-2.272649000 C 0.929588000 3.559810000-0.501608000 C 3.608486000 2.680147000 0.897741000 H 5.012851000 3.206740000-1.834480000 H 4.503625000 3.085997000-3.514353000 H 3.679337000 4.206989000-2.430391000 H 4.701938000 0.613992000-1.540883000 H 3.217630000-0.115245000-2.155769000 H 4.355773000 0.655218000-3.270253000 C 1.364086000 4.847849000-1.234280000 C -0.326959000 2.992520000-1.199986000 C 0.477037000 3.946571000 0.924725000 C 3.029478000 2.373185000 2.299760000 C 4.867956000 1.799553000 0.741493000 C 4.051078000 4.158230000 0.862262000 H 2.256627000 5.305470000-0.801113000 H 1.545038000 4.687587000-2.299316000 H 0.550480000 5.581625000-1.154633000 H -0.740335000 2.143652000-0.644265000 H -1.092795000 3.780380000-1.224882000 H -0.157851000 2.663984000-2.224469000 H -0.403648000 4.596491000 0.832895000 H 0.177879000 3.075658000 1.514485000 H 1.231701000 4.514649000 1.473889000 H 2.198683000 3.024011000 2.570759000 H 2.679354000 1.341430000 2.378843000 H 3.823505000 2.529662000 3.043651000 H 5.446390000 2.038365000-0.153790000 H 5.523449000 1.980219000 1.603891000 H 4.628581000 0.733418000 0.729752000 H 4.828056000 4.307679000 1.624641000 H 4.478902000 4.453496000-0.098451000 H 3.236355000 4.845889000 1.099764000 P -4.037751000-0.076798000 0.079420000 C -4.881661000-0.554572000-1.631767000 C -4.530246000-1.437574000 1.402402000 C -4.808380000 1.642334000 0.618711000 C -6.420348000-0.395417000-1.671363000 C -4.316964000 0.323538000-2.776591000 C -4.554500000-2.030158000-1.956803000 C -3.551948000-2.624391000 1.235808000 C -4.339251000-0.907810000 2.840203000 C -5.978376000-1.963765000 1.291539000 C -4.768022000 2.629133000-0.569238000 C -6.267262000 1.536845000 1.120440000 C -3.972651000 2.296538000 1.736774000 H -6.943733000-0.959758000-0.898941000 H -6.736760000 0.648550000-1.613736000 ps14

H -6.765799000-0.775382000-2.642171000 H -3.234125000 0.432308000-2.740261000 H -4.559105000-0.163723000-3.729498000 H -4.768968000 1.315063000-2.801723000 H -4.902912000-2.239050000-2.976210000 H -3.483103000-2.235784000-1.933435000 H -5.067968000-2.730102000-1.294401000 H -3.590106000-3.083035000 0.246797000 H -2.520037000-2.316675000 1.427512000 H -3.815750000-3.395981000 1.971781000 H -5.078397000-0.152319000 3.116589000 H -4.473929000-1.754065000 3.526943000 H -3.338688000-0.504334000 3.003828000 H -6.145282000-2.664552000 2.120105000 H -6.727042000-1.172988000 1.383052000 H -6.165995000-2.514658000 0.368072000 H -3.782697000 2.667466000-1.044069000 H -5.517884000 2.412103000-1.331725000 H -4.986026000 3.632939000-0.182645000 H -6.342802000 1.003686000 2.070682000 H -6.639561000 2.555274000 1.295699000 H -6.943074000 1.063494000 0.407866000 H -3.887253000 1.686519000 2.634002000 H -2.960418000 2.528361000 1.404081000 H -4.467991000 3.237322000 2.014185000 C 5.602086000-3.261822000-1.014943000 C 2.906954000-2.643337000-1.486487000 H 6.645595000-3.498640000-0.819444000 H 1.865019000-2.407463000-1.673908000 C 3.663160000-3.272539000-2.452225000 C 5.026240000-3.577946000-2.223587000 H 5.610632000-4.065936000-2.998722000 H 3.204640000-3.533121000-3.402230000 H 5.109868000-1.615188000 3.262611000 O 2.499146000-0.969282000 3.059769000 C 2.977501000-0.920673000 4.396645000 H 3.803674000-0.206126000 4.504298000 H 2.129216000-0.584002000 4.993638000 H 3.300827000-1.910247000 4.743099000 Br 0.595918000-2.298424000 0.930296000 I -0.901684000-1.027985000-2.468511000 B3LYP optimization 0.920604 (Hartree/Particle) Thermal correction to Energy= 0.978709 Thermal correction to Enthalpy= 0.979653 Thermal correction to Gibbs Free Energy= 0.829095 Sum of electronic and zero-point Energies= -7536.451291 Sum of electronic and thermal Energies= -7536.393187 Sum of electronic and thermal Enthalpies= -7536.392243 Sum of electronic and thermal Free Energies= -7536.542801 CPCM (Benzene) M06L/def2TZVP E = -7832.1334572 CPCM (Benzene) M062X/def2TZVP E = -7831.233538 CPCM (Benzene) BP86/def2TZVP E = -7833.0756058 CPCM (Benzene) B3LYP/def2TZVP E = -7832.3961986 CPCM (Benzene) wb97xd/def2tzvp E = -7832.0032259 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd, I) E = -7545.3672112 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd, I) E = -7544.7235177 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd, I) E = -7546.4150302 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd, I) E = -7545.3594477 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd, I) E = -7545.7257019 BP86-D3 correction = -0.3386352 B3LYP-D3 correction = -0.3371677 ωb97xd optimization 0.933771 (Hartree/Particle) Thermal correction to Energy= 0.989388 Thermal correction to Enthalpy= 0.990332 Thermal correction to Gibbs Free Energy= 0.846692 Sum of electronic and zero-point Energies= -7536.109167 Sum of electronic and thermal Energies= -7536.053550 Sum of electronic and thermal Enthalpies= -7536.052606 Sum of electronic and thermal Free Energies= -7536.196246 ps15

CPCM (Benzene) M06L/def2TZVP E = -7832.14391275 CPCM (Benzene) M062X/def2TZVP E = -7831.24419743 CPCM (Benzene) wb97xd/def2tzvp E = -7832.01663379 CPCM (Benzene) BP86/def2TZVP E = -7833.07134513 CPCM (Benzene) B3LYP/def2TZVP E = -7832.39008228 CPCM (Benzene) M06L/6-311++G(d,p) with SDD (for Pd, I) E = -7545.37466641 CPCM (Benzene) M062X/6-311++G(d,p) with SDD (for Pd, I) E = -7544.73088849 CPCM (Benzene) wb97xd/6-311++g(d,p) with SDD (for Pd, I) E = -7545.37006302 CPCM (Benzene) BP86/6-311++G(d,p) with SDD (for Pd, I) E = -7546.407656 CPCM (Benzene) B3LYP/6-311++G(d,p) with SDD (for Pd, I) E = -7545.71642188 BP86-D3 correction = -0.35204214 B3LYP-D3 correction = -0.35065605 Pd -1.343827000 0.019962000-0.055583000 P -3.714909000-0.162222000-0.011787000 C -4.146741000-1.015921000 1.686671000 C -4.608491000 1.569079000-0.089984000 C -4.383389000-1.268637000-1.469619000 Br 0.000013000-2.180467000 0.000030000 Pd 1.343841000 0.019974000 0.055730000 P 3.714920000-0.162214000 0.011678000 C 4.608498000 1.569090000 0.089869000 C 4.383555000-1.268689000 1.469394000 C 4.146587000-1.015834000-1.686861000 C -3.971770000 2.418688000-1.216448000 H -4.398297000 3.429457000-1.166742000 H -2.889832000 2.505033000-1.093896000 H -4.170923000 2.033646000-2.216387000 C -6.133284000 1.511986000-0.323016000 H -6.660494000 0.922080000 0.430176000 H -6.533037000 2.534065000-0.276616000 H -6.390527000 1.115826000-1.308863000 C -4.337667000 2.337784000 1.222685000 H -4.865025000 1.917125000 2.081677000 H -3.268775000 2.387620000 1.451997000 H -4.695440000 3.368056000 1.099127000 C -3.234768000-0.398982000 2.776611000 H -3.429862000 0.657561000 2.961215000 H -3.409139000-0.935759000 3.719029000 H -2.176590000-0.508013000 2.516730000 C -5.617467000-0.900530000 2.135929000 H -5.742519000-1.458330000 3.073881000 H -5.915588000 0.131332000 2.336964000 H -6.317894000-1.323894000 1.411318000 C -3.768381000-2.512220000 1.623254000 H -2.735823000-2.656965000 1.291847000 H -3.851065000-2.929488000 2.635339000 H -4.432989000-3.095724000 0.981993000 C -4.361799000-0.456274000-2.783098000 H -4.552162000-1.144278000-3.616979000 H -5.134307000 0.314639000-2.821284000 H -3.387062000 0.010590000-2.957877000 C -3.405504000-2.446529000-1.690715000 H -3.340648000-3.125701000-0.841020000 H -3.759257000-3.029532000-2.552034000 H -2.395034000-2.093287000-1.910839000 C -5.804560000-1.833126000-1.262707000 H -6.096221000-2.390282000-2.163406000 H -5.856961000-2.532072000-0.424443000 H -6.554602000-1.054475000-1.105030000 C 4.337578000 2.337843000-1.222753000 H 3.268671000 2.387674000-1.451993000 H 4.695347000 3.368114000-1.099176000 H 4.864887000 1.917225000-2.081795000 C 6.133307000 1.511996000 0.322794000 H 6.533054000 2.534078000 0.276392000 H 6.390620000 1.115813000 1.308614000 H 6.660466000 0.922111000-0.430449000 ps16

C 3.971848000 2.418653000 1.216406000 H 2.889901000 2.504998000 1.093926000 H 4.171067000 2.033576000 2.216318000 H 4.398368000 3.429426000 1.166710000 C 3.234438000-0.398917000-2.776668000 H 3.429444000 0.657643000-2.961265000 H 3.408724000-0.935653000-3.719125000 H 2.176299000-0.508022000-2.516658000 C 3.768322000-2.512158000-1.623445000 H 2.735814000-2.656974000-1.291916000 H 3.850907000-2.929389000-2.635553000 H 4.433043000-3.095643000-0.982284000 C 5.617248000-0.900343000-2.136302000 H 5.742215000-1.458109000-3.074286000 H 5.915282000 0.131542000-2.337346000 H 6.317793000-1.323686000-1.411792000 C 5.804709000-1.833160000 1.262316000 H 6.096462000-2.390355000 2.162961000 H 5.857031000-2.532067000 0.424016000 H 6.554731000-1.054497000 1.104601000 C 3.405700000-2.446597000 1.690539000 H 3.340762000-3.125731000 0.840818000 H 3.759545000-3.029637000 2.551794000 H 2.395250000-2.093372000 1.910783000 C 4.362094000-0.456383000 2.782911000 H 4.552554000-1.144420000 3.616742000 H 5.134595000 0.314539000 2.821049000 H 3.387369000 0.010461000 2.957813000 I -0.000034000 2.437397000 0.000236000 B3LYP optimization 0.748822 (Hartree/Particle) Thermal correction to Energy= 0.794836 Thermal correction to Enthalpy= 0.795780 Thermal correction to Gibbs Free Energy= 0.670893 Sum of electronic and zero-point Energies= -4465.467436 Sum of electronic and thermal Energies= -4465.421422 Sum of electronic and thermal Enthalpies= -4465.420478 Sum of electronic and thermal Free Energies= -4465.545364 CPCM (Benzene) M06L/def2-TZVP E = -4758.1726033 ωb97xd optimization 0.759125 (Hartree/Particle) Thermal correction to Energy= 0.803287 Thermal correction to Enthalpy= 0.804231 Thermal correction to Gibbs Free Energy= 0.683590 Sum of electronic and zero-point Energies= -4465.237798 Sum of electronic and thermal Energies= -4465.193635 Sum of electronic and thermal Enthalpies= -4465.192691 Sum of electronic and thermal Free Energies= -4465.313333 CPCM (Benzene) M06L/def2-TZVP E = -4758.17837445 Ox. Add. TS-3 C -5.628790000-1.965432000-0.817934000 C -3.589917000-2.028424000 0.557093000 C -2.849455000-1.593807000-0.592921000 C -3.484837000-1.463121000-1.837844000 C -4.890101000-1.618620000-1.927113000 C -5.013349000-2.190872000 0.437668000 Pd -1.327622000-0.019567000-0.240180000 Pd 1.561844000-0.108625000-0.027039000 Br 1.125083000 0.460797000-2.441249000 H -6.705077000-2.090761000-0.905598000 H -2.437784000 2.322070000 4.056319000 ps17

C -1.920143000 2.456819000 3.097267000 C -2.981838000 2.450877000 1.974287000 H -1.206768000 1.634237000 2.991138000 H -1.368937000 3.397474000 3.163333000 P -2.097007000 2.323956000 0.240455000 C -3.908626000 3.669403000 2.167702000 C -3.806296000 1.164566000 2.195693000 C -0.685777000 3.673833000 0.202301000 C -3.390944000 2.796956000-1.140549000 H -4.784602000 3.637716000 1.515365000 H -4.280850000 3.660506000 3.201289000 H -3.402998000 4.624531000 2.013611000 H -4.604499000 1.020470000 1.467026000 H -3.167371000 0.280195000 2.177621000 H -4.274192000 1.219201000 3.188035000 C -1.066301000 5.043802000 0.805526000 C 0.537657000 3.126567000 0.969940000 C -0.205164000 3.902402000-1.248099000 C -2.826926000 2.319813000-2.500722000 C -4.701465000 2.014529000-0.909470000 C -3.749024000 4.294173000-1.253263000 H -1.939360000 5.496206000 0.329873000 H -1.249245000 4.994958000 1.881387000 H -0.222456000 5.731216000 0.656529000 H 0.906696000 2.197777000 0.520323000 H 1.343239000 3.871781000 0.910457000 H 0.349319000 2.928123000 2.024293000 H 0.701870000 4.520778000-1.209608000 H 0.059844000 2.966781000-1.747742000 H -0.930073000 4.444789000-1.859346000 H -1.936148000 2.865707000-2.810395000 H -2.572153000 1.256976000-2.484185000 H -3.595009000 2.481210000-3.270637000 H -5.271053000 2.383260000-0.053599000 H -5.338555000 2.138877000-1.795567000 H -4.527243000 0.944563000-0.779522000 H -4.519505000 4.409414000-2.028252000 H -4.157896000 4.705021000-0.327183000 H -2.900282000 4.911004000-1.556568000 P 4.062327000-0.043048000-0.029510000 C 4.892779000-0.337041000 1.729352000 C 4.581309000-1.531587000-1.194097000 C 4.837721000 1.610401000-0.741902000 C 6.429238000-0.156940000 1.769364000 C 4.302652000 0.641948000 2.774035000 C 4.577177000-1.774398000 2.204097000 C 3.610655000-2.701257000-0.909873000 C 4.392779000-1.158526000-2.680771000 C 6.033147000-2.027504000-1.019450000 C 4.785678000 2.719004000 0.332510000 C 6.300614000 1.458164000-1.217638000 C 4.007485000 2.137384000-1.928858000 H 6.967103000-0.786857000 1.060020000 H 6.736097000 0.879967000 1.615901000 H 6.767614000-0.438438000 2.775556000 H 3.214518000 0.679210000 2.752315000 H 4.594431000 0.287803000 3.771191000 H 4.691829000 1.654243000 2.667854000 H 4.913064000-1.869773000 3.244680000 H 3.508449000-1.994691000 2.189604000 H 5.106968000-2.535163000 1.626842000 H 3.640402000-3.052283000 0.122406000 H 2.580260000-2.417695000-1.140741000 H 3.883110000-3.544755000-1.558530000 H 5.131260000-0.436045000-3.036111000 H 4.528689000-2.072671000-3.273926000 H 3.392078000-0.775413000-2.888063000 H 6.210021000-2.818479000-1.760328000 H 6.773842000-1.244969000-1.200844000 H 6.223594000-2.464283000-0.037664000 H 3.799703000 2.796654000 0.800225000 H 5.536699000 2.592889000 1.114173000 H 4.993703000 3.678124000-0.158917000 H 6.387352000 0.821546000-2.100627000 H 6.669157000 2.452576000-1.503783000 H 6.972135000 1.072306000-0.450393000 ps18

H 3.920311000 1.431348000-2.752455000 H 2.995644000 2.407961000-1.625818000 H 4.505577000 3.040001000-2.309308000 C -5.768583000-2.597231000 1.571147000 C -2.990456000-2.317893000 1.812676000 H -6.845859000-2.701889000 1.463100000 H -1.918074000-2.199753000 1.923626000 C -3.751342000-2.729478000 2.885966000 C -5.155300000-2.864768000 2.772768000 H -5.741922000-3.182363000 3.630315000 H -3.263400000-2.945206000 3.832512000 H -5.388441000-1.465445000-2.877484000 O -2.710560000-1.188072000-2.917526000 C -3.290298000-1.179545000-4.214629000 H -4.013738000-0.362325000-4.328222000 H -2.457559000-1.021128000-4.900748000 H -3.777137000-2.136081000-4.442708000 I -0.676093000-2.588619000-0.812504000 I 0.884441000-0.782859000 2.541828000 B3LYP optimization 0.920248 (Hartree/Particle) Thermal correction to Energy= 0.978549 Thermal correction to Enthalpy= 0.979493 Thermal correction to Gibbs Free Energy= 0.827878 Sum of electronic and zero-point Energies= -4976.429292 Sum of electronic and thermal Energies= -4976.370991 Sum of electronic and thermal Enthalpies= -4976.370046 Sum of electronic and thermal Free Energies= -4976.521662 CPCM (Benzene) M06L/def2-TZVP E = -5555.9571976 ωb97xd optimization 0.933167 (Hartree/Particle) Thermal correction to Energy= 0.989125 Thermal correction to Enthalpy= 0.990069 Thermal correction to Gibbs Free Energy= 0.845462 Sum of electronic and zero-point Energies= -4976.074910 Sum of electronic and thermal Energies= -4976.018953 Sum of electronic and thermal Enthalpies= -4976.018009 Sum of electronic and thermal Free Energies= -4976.162615 CPCM (Benzene) M06L/def2-TZVP E = -5555.96756808 C -4.578657000-3.953524000-0.485132000 C -3.597533000-2.254852000 0.996678000 C -3.089580000-1.579894000-0.149846000 C -3.293110000-2.119113000-1.412324000 C -4.045743000-3.309490000-1.579488000 C -4.369894000-3.458672000 0.825045000 Pd -1.887059000 0.039861000 0.016300000 Pd 2.437633000-0.575483000 0.014762000 I 0.659609000 1.584995000 0.384774000 H -5.158512000-4.863315000-0.620025000 H -6.871868000 0.384313000 1.540310000 C -5.868614000 0.827426000 1.491667000 C -5.586020000 1.204510000 0.019831000 H -5.167691000 0.077059000 1.864948000 H -5.863665000 1.681461000 2.170253000 P -3.708057000 1.755234000-0.175891000 C -6.601126000 2.283144000-0.425540000 C -5.901449000-0.069127000-0.800831000 C -3.383809000 3.107657000 1.215934000 C -3.522667000 2.600720000-1.927466000 ps19

H -6.609344000 2.413447000-1.510642000 H -7.604610000 1.940633000-0.139820000 H -6.448429000 3.257895000 0.035754000 H -5.608632000-0.007600000-1.847391000 H -5.435726000-0.951549000-0.370349000 H -6.989022000-0.219355000-0.771393000 C -4.557145000 4.066519000 1.516943000 C -3.006532000 2.344649000 2.508466000 C -2.177764000 4.004403000 0.863083000 C -2.016878000 2.693086000-2.259751000 C -4.146961000 1.699334000-3.016010000 C -4.150871000 4.005495000-2.049551000 H -4.856799000 4.647237000 0.640359000 H -5.439828000 3.569250000 1.920950000 H -4.219706000 4.782619000 2.278080000 H -2.094547000 1.755495000 2.369771000 H -2.814035000 3.075709000 3.305178000 H -3.794103000 1.675493000 2.859005000 H -1.941247000 4.614477000 1.744771000 H -1.282682000 3.433975000 0.622522000 H -2.382735000 4.694690000 0.042505000 H -1.457663000 3.331478000-1.575360000 H -1.547363000 1.704895000-2.258593000 H -1.909731000 3.117085000-3.267332000 H -5.239011000 1.695706000-2.987373000 H -3.855169000 2.101822000-3.995254000 H -3.781232000 0.670520000-2.956922000 H -3.999183000 4.360310000-3.077766000 H -5.225833000 4.008183000-1.862409000 H -3.688024000 4.739972000-1.388286000 P 4.702882000 0.521639000 0.181461000 C 6.241126000-0.711077000 0.112489000 C 4.828811000 1.721489000-1.353669000 C 4.919252000 1.560475000 1.830728000 C 7.594145000-0.068783000 0.499662000 C 6.007386000-1.903869000 1.071804000 C 6.401309000-1.291011000-1.312378000 C 4.217402000 0.975164000-2.563624000 C 3.971849000 2.986641000-1.136727000 C 6.254799000 2.193953000-1.711222000 C 5.180281000 0.607174000 3.018827000 C 6.052430000 2.609835000 1.770251000 C 3.617333000 2.305264000 2.184617000 H 7.850041000 0.810718000-0.094100000 H 7.652881000 0.196039000 1.557249000 H 8.376030000-0.818308000 0.319634000 H 5.077921000-2.429216000 0.856010000 H 6.831472000-2.615077000 0.925840000 H 6.016470000-1.615793000 2.122487000 H 7.174121000-2.069497000-1.268843000 H 5.486469000-1.760687000-1.671794000 H 6.739313000-0.549664000-2.038771000 H 4.746392000 0.056335000-2.819540000 H 3.169899000 0.716060000-2.380731000 H 4.255955000 1.639316000-3.437539000 H 4.378834000 3.652114000-0.371686000 H 3.960441000 3.550632000-2.078844000 H 2.936210000 2.752194000-0.887229000 H 6.181864000 2.869111000-2.574205000 H 6.727043000 2.755816000-0.901544000 H 6.919770000 1.378971000-1.997953000 H 4.454064000-0.211242000 3.055938000 H 6.185989000 0.184786000 3.020690000 H 5.072287000 1.183454000 3.946640000 H 5.826761000 3.422666000 1.075755000 H 6.150063000 3.061512000 2.766757000 H 7.024575000 2.194437000 1.506822000 H 3.274011000 2.986573000 1.407006000 H 2.805725000 1.612403000 2.410196000 H 3.805271000 2.903335000 3.086584000 C -4.884067000-4.126773000 1.970338000 C -3.360833000-1.804297000 2.329417000 H -5.467474000-5.033017000 1.821562000 H -2.750436000-0.916985000 2.469243000 C -3.867664000-2.480531000 3.416675000 C -4.644780000-3.652421000 3.238735000 ps20

H -5.039637000-4.177102000 4.104483000 H -3.664013000-2.117811000 4.420843000 H -4.210395000-3.713632000-2.572735000 O -2.770044000-1.433010000-2.483681000 C -2.556189000-2.138711000-3.699518000 H -3.498892000-2.361443000-4.217499000 H -1.955092000-1.476632000-4.325723000 H -2.005808000-3.070815000-3.525423000 I 0.034505000-1.943106000 0.055416000 Br 3.241496000-2.771451000-0.898193000 B3LYP optimization 0.921859 (Hartree/Particle) Thermal correction to Energy= 0.980408 Thermal correction to Enthalpy= 0.981352 Thermal correction to Gibbs Free Energy= 0.828514 Sum of electronic and zero-point Energies= -4976.466776 Sum of electronic and thermal Energies= -4976.408227 Sum of electronic and thermal Enthalpies= -4976.407283 Sum of electronic and thermal Free Energies= -4976.560122 CPCM (Benzene) M06L/def2-TZVP E = -5555.9750027 ωb97xd optimization 0.936089 (Hartree/Particle) Thermal correction to Energy= 0.991931 Thermal correction to Enthalpy= 0.992875 Thermal correction to Gibbs Free Energy= 0.848576 Sum of electronic and zero-point Energies= -4976.106540 Sum of electronic and thermal Energies= -4976.050698 Sum of electronic and thermal Enthalpies= -4976.049754 Sum of electronic and thermal Free Energies= -4976.194053 CPCM (Benzene) M06L/def2-TZVP E = -5555.98490809 I4 C 4.234772000 4.124644000 0.374923000 C 3.577363000 2.025763000 1.474712000 C 2.963257000 1.612194000 0.259335000 C 2.945960000 2.463450000-0.834508000 C 3.595953000 3.723273000-0.776481000 C 4.240443000 3.303939000 1.529151000 Pd 1.849131000-0.068408000 0.196736000 Pd -2.198718000 0.414751000 0.182470000 I -0.519068000-1.802469000 0.837018000 H 4.733046000 5.090396000 0.411201000 H 7.022805000-0.445898000 0.882330000 C 6.036799000-0.928772000 0.883541000 C 5.521316000-0.957725000-0.574008000 H 5.390026000-0.336170000 1.535402000 H 6.167161000-1.919002000 1.322691000 P 3.652629000-1.561336000-0.614196000 C 6.467526000-1.837413000-1.425156000 C 5.672348000 0.492915000-1.092390000 C 3.585008000-3.221485000 0.436064000 C 3.196633000-1.969444000-2.468287000 H 6.298439000-1.699207000-2.495902000 H 7.498499000-1.518583000-1.222384000 H 6.408376000-2.902200000-1.203390000 H 5.181996000 0.679329000-2.045892000 H 5.297895000 1.216718000-0.372953000 H 6.745176000 0.683961000-1.228739000 C 4.815122000-4.147672000 0.311795000 C 3.409285000-2.807484000 1.916359000 C 2.361224000-4.086663000 0.063278000 C 1.657702000-2.064880000-2.571227000 C 3.616624000-0.802491000-3.389275000 C 3.818754000-3.268274000-3.027810000 H 4.977528000-4.491707000-0.713406000 ps21

H 5.739887000-3.701007000 0.678099000 H 4.627299000-5.039266000 0.924505000 H 2.483011000-2.243958000 2.061555000 H 3.350765000-3.714680000 2.532375000 H 4.237044000-2.205183000 2.294377000 H 2.275944000-4.888088000 0.808847000 H 1.424464000-3.532466000 0.081461000 H 2.461766000-4.567848000-0.911582000 H 1.229714000-2.867544000-1.970955000 H 1.180761000-1.127221000-2.270618000 H 1.392292000-2.255938000-3.619704000 H 4.699021000-0.735085000-3.522100000 H 3.184226000-0.986907000-4.381770000 H 3.235028000 0.158904000-3.035713000 H 3.507143000-3.370683000-4.075841000 H 4.910239000-3.259094000-3.015872000 H 3.479455000-4.165948000-2.507601000 P -4.478336000-0.480954000 0.337772000 C -5.880373000 0.834060000-0.078252000 C -4.712015000-2.015190000-0.834868000 C -4.770940000-1.033913000 2.199031000 C -7.277012000 0.461321000 0.471640000 C -5.492430000 2.212185000 0.510285000 C -6.030224000 1.020277000-1.605759000 C -4.047760000-1.658385000-2.185319000 C -3.964456000-3.248059000-0.283271000 C -6.176881000-2.442338000-1.075832000 C -4.923394000 0.216009000 3.095982000 C -5.998044000-1.953543000 2.396439000 C -3.540490000-1.782196000 2.751999000 H -7.633977000-0.510439000 0.124166000 H -7.327305000 0.480962000 1.561534000 H -7.987154000 1.215444000 0.108087000 H -4.546988000 2.578041000 0.109613000 H -6.272574000 2.930464000 0.225551000 H -5.431803000 2.216505000 1.598260000 H -6.705385000 1.869718000-1.771396000 H -5.085468000 1.260840000-2.091962000 H -6.479197000 0.156372000-2.099717000 H -4.512098000-0.807076000-2.684717000 H -2.986074000-1.430186000-2.054957000 H -4.131744000-2.525435000-2.854079000 H -4.426440000-3.656525000 0.618485000 H -4.004504000-4.033985000-1.048797000 H -2.911784000-3.044740000-0.080744000 H -6.168041000-3.331684000-1.719762000 H -6.692607000-2.719195000-0.152870000 H -6.771928000-1.685740000-1.588599000 H -4.102877000 0.925842000 2.948633000 H -5.870075000 0.740576000 2.958192000 H -4.887094000-0.111447000 4.142827000 H -5.858554000-2.933625000 1.933558000 H -6.121573000-2.125930000 3.474044000 H -6.931886000-1.530335000 2.027556000 H -3.269640000-2.670081000 2.181596000 H -2.662810000-1.136570000 2.804901000 H -3.777595000-2.106413000 3.774148000 C 4.862261000 3.716065000 2.739631000 C 3.554502000 1.241084000 2.666421000 H 5.361537000 4.682555000 2.760415000 H 3.026595000 0.292291000 2.648020000 C 4.159764000 1.675964000 3.824548000 C 4.829163000 2.924420000 3.863837000 H 5.304427000 3.255912000 4.783069000 H 4.117812000 1.059827000 4.719081000 H 3.592882000 4.372905000-1.645682000 O 2.318289000 2.025554000-1.973521000 C 1.784876000 3.000654000-2.865680000 H 2.572704000 3.483751000-3.459637000 H 1.111651000 2.459016000-3.531738000 H 1.211761000 3.758528000-2.321303000 Br -0.026395000 1.653073000 0.693313000 I -2.492119000 2.264187000-1.840681000 ps22