Stereochemical nversion in Difunctionalized Pillar[5]arenes Nathan L. Strutt, Severin T. Schneebeli, J. Fraser Stoddart* Department of hemistry, Northwestern University, Evanston, L U.S.A. stoddart@northwestern.edu Supporting nformation ontents S1. General Methods S2 S2. 1H NMR Spectra of ompounds 2 and 3 S3 S3. Variable Temperature 1H NMR Spectra of 1 S4 6 S4. Variable Temperature 1H NMR Spectra of 2 S7 8 S5. Variable Temperature 1H NMR Spectra of 3 S9 10 S6. 2-D NMR Experiments with 1 S11 14 S7. 2-D NMR Experiments with 2 S15 17 S8. 2-D NMR Experiments with 3 S18 21 S9. Simulated 1H NMR spectra of 1 S22 23 S10. Eyring Plot for 3 S24 S11. X-Ray rystallography of 3 S25 S12. Molecular Mechanics alculations S26 S13. Quantum Mechanical alculations S27 S14. DFT-ptimized Structures and Energies S28 51
S1. General Methods Analytical thin-layer chromatography (TL) was carried out using glass plates, precoated with silica gel 60 and fluorescent indicator (Whatman LK6F). The plates were inspected by UV light (254 nm). Flash chromatography was carried out using silica gel 60 (Silicycle) as the stationary phase. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker Avance 500 and 600 MHz spectrometers, with working frequencies of 499.373 and 600.168 MHz for 1 H, and 125.579 and 150.928 MHz for 13 nuclei, respectively. hemical shifts are reported in ppm relative to the signals corresponding to the residual non-deuterated solvent and coupling constants were recorded in Hertz (Hz). Temperatures for VT 1 H NMR experiments were calibrated using either 100% MeH or 100% ethylene glycol. Simulated 1 H NMR spectra were created using inmr version 3.2.1. Single crystal X-ray data was collected on a Bruker Kappa APEX D Diffractometer equipped with a ukα microsource with Quazar optics. Molecular mechanics calculations were performed with the PLS-2005 force field using the program MacroModel software package. alculations were performed with the chloroform GB/SA solvation model. Density functional theory (DFT) calculations were performed with the B3LYP functional using the Jaguar software package. Single point calculations were conducted with the Poisson-Boltzmann continuum-solvation model implemented in Jaguar using either the 6-311G**++ or LAV3P**++ basis set. Geometry optimizations and frequency calculations were conducted with either the 6-31G* or LAVP*basis set. Default grids and SF convergence criteria as implemented in Jaguar were used. S2
S2. 1 H NMR Spectra of ompounds 2 and 3 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 +V Hl3 H$ H" H% H# H! H2l2 Hc+d He Ha+b 7.0 6.5 6.0 5.5 5.0 4.5 4.0 δ (ppm) Figure S1. 1 H NMR (600 MHz, 318 K, Dl 3 ) spectrum of compound 2. H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 +V H Hl3 H! H" H# H$ H2l2 Hb Hc+d Ha He 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 δ (ppm) Figure S2. 1 H NMR (600 MHz, 318 K, Dl 3 ) spectrum of compound 3. S3
S3. Variable Temperature 1 H NMR Spectra of 1 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 328 318 308 298 288 Temperature (K) 278 268 258 248 238 228 218 δ (ppm) 7.0 6.0 5.0 4.0 3.0 Figure S3. Variable temperature (VT) 1 H NMR (600 MHz, Dl 3 ) spectra of 1. S4
H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 358 1 348 338 328 318 Temperature (K) 308 298 288 278 268 258 248 238 δ (ppm) 7.0 6.0 5.0 4.0 3.0 Figure S4. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 1. S5
H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 298 Ha + Hb 288 278 268 Temperature (K) 258 248 238 228 218 213 208 δ (ppm) 3.8 3.6 3.4 3.2 3.0 Figure S5. Variable temperature (VT) 1 H NMR (600 MHz, 4:1 Dl 3 / D 3 D) spectra of 1. S6
S4. Variable Temperature 1 H NMR Spectra of 2 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 328 318 308 Temperature (K) 298 288 278 268 258 248 238 228 7.0 6.0 5.0 4.0 δ (ppm) Figure S6. Variable temperature (VT) 1 H NMR (600 MHz, Dl 3 ) spectra of 2. S7
H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 Temperature (K) 298 258 7.0 6.0 5.0 4.0 3.0 Figure S7. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 2. S8
S5. Variable Temperature 1 H NMR Spectra of 3 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 328 318 308 298 Temperature (K) 288 278 268 258 248 238 228 8.0 7.0 6.0 5.0 4.0 δ (ppm) Figure S8. Variable temperature 1 H NMR (600 MHz, Dl 3 ) spectra of 3. S9
H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 358 348 338 328 318 Temperature (K) 308 298 288 278 268 258 248 238 8.0 7.0 6.0 5.0 4.0 δ (ppm) Figure S9. Variable temperature (VT) 1 H NMR (600 MHz, Dl 2 Dl 2 ) spectra of 3. S10
S6. 2-D NMR Experiments with 1 H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 V + + He Hc+d Ha Hb 2D HSQ 233 K Dl3 600 MHz 20 30 40 60 40 80 100 50 120 60 7.0 6.0 5.0 4.0! (ppm) 4.5 4.0 3.5 3.0! (ppm) Figure S10. Phase-sensitive multiplicity-edited 2-D HSQ spectrum (600 MHz, 233 K, Dl 3 ) of 1 (left). Enlargement of aliphatic section of HSQ spectrum (right). Red crosspeaks indicate H 2 groups and blue crosspeaks indicate H 3 groups. S11
H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 V + + He Hc+d Ha Hb 2D NESY 228 K Dl3 600 MHz 3.0 4.0 5.0 H! H% H$ H# H" (H! Ha) (H% Ha) (H% ) (H# V) (H" ) (H! ) (H" Hc+d) (H$ ) (H" ) (H! Hb) (H% Hb) 6.6 6.8 7.0 6.0 7.2 Hl3 7.0 H (H Ha) (H ) (H Hb) 7.4 7.6 8.0 7.0 6.0 5.0 4.0! (ppm) 4.2 4.0 3.8 3.6 3.4! (ppm) Figure S11. 2-D NESY Spectrum (600 MHz, 228 K, Dl 3 ) of 1 (left). Enlargement of the bottom right section of the spectrum (blue box in full spectrum) with annotated crosspeaks (right). S12
H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 Hc+d He Ha+b V 2D HSQ 348 K Dl2Dl2 600 MHz 40 30 35 60 40 80 45 100 50 55 120 60 7.0 6.0 5.0 4.0! (ppm) 4.0 3.8 3.6 3.4 3.2! (ppm) Figure S12. 2-D HSQ Spectrum (600 MHz, 348 K, Dl 2 Dl 2 ) of 1 (left). Enlargement of aliphatic section of HSQ spectrum (right). S13
H % H 3 H 3 H H 3 V H 3 H H % H 3 V H 3 H 3 H 3 1 Hc+d He V Ha+b 2D NESY 350 K Dl2Dl2 600 MHz 4.0 H (H ) (H Ha+b) 6.4 6.5 (H$ He) (H$ V) 5.0 H$ (H% Ha+b) 6.6 H% H! H# (H# Hc+d) (H! Ha+b) (H$ ) 6.7 6.0 H" (H" Hc+d) (H! ) (H# V) 6.8 7.0 (H" ) (H" ) 6.9 7.0 6.0 5.0 4.0! (ppm) 3.9 3.7 3.5! (ppm) Figure S13. 2-D NESY Spectrum (600 MHz, 350 K, Dl 2 Dl 2 ) of 1 (left). Enlargement of the bottom right section (blue box in full spectrum) with annotated crosspeaks (right). S14
S7. 2-D NMR Experiments with 2 H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 V He Hc+d Ha+b 2D HSQ 318 K Dl3 600 MHz 40 30 60 40 80 100 50 120 60 7.0 6.0 5.0 4.0! (ppm) 4.2 4.0 3.8 3.6 3.4! (ppm) Figure S14. 2-D HSQ Spectrum (600 MHz, 318 K, Dl 3 ) of 2 (left). Enlargement of aliphatic section of HSQ spectrum (right). S15
H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 H# H! Hl3 H$ H" H% 2D NESY 318 K Dl2Dl2 600 MHz 3.0 3.0 ( H") 4.0 5.0 V + Hc+d Ha+b He (V H#) ( H$) (He H$) (Ha+b H!) (Ha+b H%) ( H!) 3.5 6.0 (Hc+d H#) (Hc+d H") 4.0 7.0 4.5 7.0 6.0 5.0 4.0! (ppm) 7.4 7.0 6.6 6.2! (ppm) Figure S15. 2-D NESY Spectrum (600 MHz, 318 K, Dl 3 ) of 2 (left). Enlargement of the top left section (blue box in full spectrum) with annotated crosspeaks (right). S16
H % H 3 H 3 H 3 V H 3 H % H 3 V H 3 H 3 H 3 2 Hc+d V He Ha+b 2D HSQ 298 K Dl2Dl2 600 MHz 20 40 30 60 80 40 100 50 120 7.0 60 6.0 5.0 4.0! (ppm) 4.2 3.8 3.6 3.4! (ppm) Figure S16. 2-D HSQ Spectrum (600 MHz, 298 K, Dl 2 Dl 2 ) of 2 (left). Enlargement of the aliphatic section of the HSQ spectrum (right). S17
S8. 2-D NMR Experiments with 3 H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 V + Hc+d Hb Ha He 2D HSQ 300 K Dl3 600 MHz 20 40 20 30 60 80 40 100 50 120 60 8.0 7.0 6.0 5.0 4.0! (ppm) 4.6 4.2 3.8 3.4! (ppm) Figure S17. 2-D HSQ Spectrum (600 MHz, 300 K, Dl 3 ) of 3 (left). Enlargement of aliphatic section of HSQ spectrum (right). S18
H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 V + Hc+d Hb Ha He 2D NESY 300 K Dl3 600 MHz 4.0 5.0 H$ H# H" Hl3 H! (H$ V) (H$ He) (H$ ) (H" ) (H# V) (H" ) (H" Hc+d) (H# Hc+d) (H! Ha) 7.0 6.0 (H! Hb) (H! ) 7.5 7.0 8.0 8.0 H (H Hb) (H ) (H Hb) 8.0 7.0 6.0 5.0 4.0! (ppm) 4.4 4.2 4.0 3.8 3.6 3.4! (ppm) Figure S18. 2-D NESY Spectrum (600 MHz, 300 K, Dl 3 ) of 3 (left). Enlargement of the bottom right section (blue box in full spectrum) showing annotated crosspeaks. S19
H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 Ha+b Hc+d He V 2D HSQ 368 K Dl2Dl2 600 MHz 40 30 35 60 40 80 45 100 50 55 120 8.0 7.0 6.0 5.0 4.0! (ppm) 4.2 4.0 3.8 3.6 3.4! (ppm) Figure S19. 2-D HSQ Spectrum (600 MHz, 368 K, Dl 2 Dl 2 ) of 3 (left). Enlargement of the aliphatic section of the HSQ spectrum (right). S20
H 3 H 3 H Br H 3 V H 3 Br H H 3 V H 3 H 3 H 3 3 Ha+b Hc+d He V 2D NESY 348 K 3.0 Dl2Dl2 600 MHz H# (H# Hc+d) (H# ) (H# V) 6.6 4.0 H$ (H$ He) (H$ ) (H# V) 6.7 5.0 H" (H" Hc+d) (H" ) 6.8 6.0 (H! Ha+b) (H" Hc+d) 6.9 H! 7.0 7.0 H (H Ha+b) (H ) (H! ) 7.1 7.0 6.0 5.0 4.0 3.0! (ppm) 4.2 4.0 3.8 3.6 3.4! (ppm) Figure S20. 2-D NESY Spectrum (600 MHz, 348 K, Dl 2 Dl 2 ) of 3 (left). Enlargement of bottom right section (blue box in full spectrum) showing annotated crosspeaks (right). S21
S9. Simulated 1 H NMR Spectra of 1 Dynamic 1 H NMR simulations were conducted for protons and on the methylene bridges of 1 using inmr (version 3.2.1). The magnetic field, B 0, for the simulated spectra was set to a frequency of 600.000 for 1 H, while the experimental spectra were conducted using a B 0 of 600.168 MHz. Figures S20 - S24 contain the experimental 1 H NMR spectra for the aliphatic portion of 1 directly above the simulated spectra at the same temperature. T = 328 K k = 119,000 s -1 Experimental Simulated 4.1 3.9 3.7 3.5 3.3 δ (ppm) Figure S21. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 328 K, Dl 3 ) of the aliphatic portion of 1. T = 298 K k = 19,800 s -1 Experimental Simulated 4.1 3.9 3.7 3.5 3.3 δ (ppm) Figure S22. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 298 K, Dl 3 ) of the aliphatic portion of 1. S22
T = 268 K k = 1057 s -1 Experimental Simulated 4.1 3.9 3.7 3.5 3.3 δ (ppm) Figure S23. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 268 K, Dl 3 ) of the aliphatic portion of 1. T = 238 K k = 33 s -1 Experimental Simulated 4.1 3.9 3.7 3.5 3.3 δ (ppm) Figure S24. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 238 K, Dl 3 ) of the aliphatic portion of 1. T = 218 K k = 6.0 s -1 Experimental Simulated 4.1 3.9 3.7 3.5 3.3 δ (ppm) Figure S25. Experimental (above) and simulated (below) 1 H NMR spectra (600 MHz, 218 K, Dl 3 ) of the aliphatic portion of 1. S23
S10. Eyring Plot for 3 Dynamic 1 H NMR simulations were conducted for protons and on the methylene bridges of 3 using the same method described for the simulation of the dynamic 1 H NMR of 1. The rates obtained through the 1H NMR simulations were used to generate an Eyring plot (Figure S26). The Eyring plot was used to calculate ΔH and ΔS for the inversion process in 3. ln (k / T) = ( 9151.7 ± 133.6) + (27.59 ± 0.44) R 2 = 0.998 H = 18.2 ± 0.3 kcal mol -1 S = 7.6 ± 0.9 cal mol -1 K -1 Figure S26. Eyring plot of the stereochemical inversion process of 3 using simulated 1 H NMR spectroscopic data to determine the rate of the process at multiple temperatures. The equation of the linear curve was used to calculate ΔH and ΔS for this process. S24
S11. X-Ray rystallography of 3 a) Methods. Single crystals of 3 were grown by slow evaporation of H 2 l 2. Data was collected at 100 K on a Bruker Kappa APEX D Diffractometer equipped with a ukα microsource with Quazar optics. The SQUEEZE function of PLATN was used to remove the contribution of disordered solvent molecules to the data. b) rystal Parameters. Formula: 43 H 44 Br 2 10, orange block, 0.066 0.130 0.170 mm 3, monoclinic, space group P2 1 /n; a = 12.5156(3), b = 31.1509(9), and c = 23.4909(7) Å; β = 104.250(2) ; V = 8876.7(4) Å 3 ; T = 100(2) K, Z = 8, ρ calc = 1.318 g cm 3, µ(u Kα) = 2.752 mm 1, F(000) = 3616; independent measured reflections = 92,194; R 1 = 0.0991 and wr 2 = 0.2635 for 14760 independent observed reflections [2θ 124, > 2σ ()]. D# 941134. Figure S27. X-Ray crystal structure of 3 with thermal ellipsoids shown at a 50% probability level. atoms are black, atoms are red, Br atoms are gold, toms are white. S25
S12. Molecular Mechanics alculations Molecular mechanics coordinate scans were performed with MacroModel to determine approximate structures for the transition states between intermediate conformations. The coordinate scans were conducted by rotating the respective aromatic unit at 1 intervals over 180 through the pillar[5]arene cavity. The PLS 2005 energies of the highest energy structures of the coordinate scans (approximate transition states) are listed in Table S1. The molecular mechanics calculations were conducted with the chloroform GB/SA solvation model implemented in Macromodel. Due to the symmetry of the system, the reverse pathways involving enantiomers of the transformations listed were assumed to have the same transition state and energy barrier, e.g. the tranformation of conformer 1 to conformer 1 a1 would have a transition state which is the enantiomer of the transformation of conformer 1* to conformer 1 a1 *. Table S1. PLS 2005 energies of approximate transition states. Transformation (1 st conformer to 2 nd conformer) Relative PLS 2005 Energy (in Hl 3 ) (kcal mol -1 ) 1 to 1 a1 12.5 1 a1 to 1 b1 17.2 1 b1 to 1 b3 * 13.1 1 a3 to 1 b3 15.6 1 a3 to 1 10.1 1 b1 to 1 b6* 12.9 1 b6 to 1 a3 11.2 1 to 1 a2 10.5 1 a2 to 1 b1 15.3 1 a2 to 1 b3 13.5 1 a3 to 1 b6 11.2 S26
S13. Quantum Mechanical alculations Density functional theory (DFT) calculations were performed with the B3LYP exchangecorrelation functional using the Jaguar software package. Geometry optimization and frequency calculations were conducted with either the 6-31G* or LAVP* basis set. Table S2 lists the lowest calculated vibrational frequency and zero point energies for each intermediate conformer and transition state. Single point calculations (Table S2) were conducted with a Poisson-Boltzmann continuum-solvation model using either the 6-311G**++ or LAV3P**++ basis set. Default grids and SF convergence criteria as implemented in Jaguar were used. Table S2. DFT calculated properties for intermediate conformers and transition states ntermediate onformer Single Point Energy (Hartrees) Zero Point Energy (Hartrees) Total Energy (Hartrees) Energy Relative to onformer 1 (kcal mol -1 ) 1-2419.1186029 0.8215605-2418.2970424 0.00 1 a2-2419.1096414 0.8197852-2418.2898562 4.51 1 b1-2419.1079247 0.8199542-2418.2879705 5.69 1 b6 * -2419.1107484 0.8206219-2418.2901265 4.34 1 a3 * -2419.1138634 0.8203972-2418.2934662 2.24 Transition State Single Point Energy (Hartrees) Zero Point Energy (Hartrees) Total Energy (Hartrees) Energy Relative to onformer 1 (kcal mol -1 ) TS 1 (1 / 1 a2 ) -2419.1019248 0.8199127-2418.2820121 9.43 TS 2 (1 a2 / 1 b1 ) -2419.0952170 0.8200848-2418.2751321 13.75 TS 3 (1 b1 / 1 b6 *) -2419.0965945 0.8193056-2418.2772889 12.39 TS 4 (1 b6 * / 1 a3 *) -2419.1008107 0.8204816-2418.2803291 10.49 TS 5 (1 a3 * / 1*) -2419.1076203 0.8204099-2418.2872103 6.17 S27
S14. DFT ptimized Structures and Energies onformer 1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.2970424 Hartrees (oordinates in Ångströms) atom x y z 14.8556980581 0.6357329080 0.7978602495 H 14.7133493774 0.8081175815-0.2747211766 H 14.6734508366-0.4305755534 0.9679680477 16.2958330021 0.9893083125 1.1540533356 16.9614078511 0.3969107302 2.2436001463 18.2728311465 0.7724952366 2.5376323072 H 18.7604126026 0.2810904861 3.3758619256 18.9555115344 1.7447769336 1.8026050812 18.2828486752 2.3522717490 0.7259562865 16.9809318114 1.9570296803 0.4150272338 H 16.4989603689 2.4358945938-0.4337333981 20.3716970841 2.1463010196 2.2022074303 H 20.8668123471 1.2746019311 2.6443661326 H 20.9524888868 2.4167850759 1.3142419058 20.4076186381 3.2858345175 3.2132045433 20.3093760863 3.0141202897 4.5810951427 H 20.2599689398 1.9760354294 4.8903925332 20.2512623643 4.0358044653 5.5315499862 20.2907460054 5.3818117080 5.1277218790 20.4236096190 5.6544393651 3.7651653071 H 20.4472380421 6.6926277568 3.4577049835 20.4836183644 4.6282626060 2.8207229805 20.1295223297 2.4705933255 7.3409642284 H 19.2577949303 1.9257890920 6.9544876134 H 20.0671171978 2.5249273459 8.4301548904 H 21.0433077704 1.9298606345 7.0597575776 20.6868387311 6.2038447959 1.0014692012 H 19.7819944294 6.7667956276 1.2621021195 H 20.7793420420 6.1454742516-0.0848635212 H 21.5649643510 6.7135921861 1.4164305679 20.1460431904 6.5128004991 6.1351240110 H 20.6494674176 7.4024785738 5.7454619367 H 20.6424706403 6.2330510213 7.0688946876 18.6892525114 6.8438360124 6.4279570027 18.0246371788 6.2446173720 7.5004001996 H 18.5860480549 5.5550330757 8.1187466302 16.6726683256 6.4916667333 7.7546892940 15.9465720369 7.3664012676 6.9318115292 16.6150209465 7.9779674445 5.8673780304 H 16.0429036906 8.6422321383 5.2302156966 17.9648352359 7.7262783273 5.6098112081 16.6906396401 5.0865221712 9.6961616381 H 17.1054276340 4.1992851745 9.1981869408 H 15.9680819232 4.7698174005 10.4520330192 H 17.5082744920 5.6337617377 10.1849565378 17.9785431496 9.2226608349 3.7390406638 H 17.1399219281 8.7464009582 3.2132478548 H 18.7116265369 9.5710393761 3.0074442233 H 17.5996912347 10.0833838796 4.3066974682 14.4647986590 7.6247029978 7.1628557070 H 14.2359024582 7.4720645803 8.2210770888 H 14.2420049615 8.6677202551 6.9222980427 13.5736858803 6.7188412528 6.3253152151 13.2527181696 5.4327912980 6.7694133631 H 13.6520469397 5.1177128520 7.7263636601 12.4690064813 4.5676678042 6.0016223870 11.9774219875 4.9780190862 4.7513883309 S28
12.2848710770 6.2690882188 4.3156132825 H 11.9133715281 6.5749348792 3.3453849315 13.0744474852 7.1325033421 5.0805441806 12.8608760544 8.8956311039 3.4710235656 H 13.1934080641 8.3082570677 2.6039983727 H 13.2191494982 9.9227055191 3.3682123928 H 11.7626117214 8.8972522249 3.4980810426 12.5933009289 2.8426139034 7.6586263977 H 12.2195058639 3.4707237921 8.4786216060 H 13.6905844310 2.8174379633 7.7014137766 H 12.2043614080 1.8285537152 7.7788759201 11.1687239303 4.0328894345 3.8736866403 H 10.5203708996 3.4165258238 4.5035362013 H 10.5258302266 4.6226410473 3.2135326080 12.0533875875 3.1216278084 3.0359559335 13.2581813865 1.0240474521 2.7619500794 13.8291564312 1.4644837767 1.5612856383 13.4671862252 2.7327402423 1.0976926053 H 13.9019275475 3.0755428979 0.1654018875 13.0816561287-0.7466403671 4.3957289702 H 13.3682691759-0.1173885269 5.2474800245 H 13.5027977891-1.7459245348 4.5229391537 H 11.9880915673-0.8142192947 4.3444860639 12.7227521915 5.2827396807 0.1583555327 H 13.8172919892 5.3698202435 0.1788569757 H 12.2847605028 6.2729388328 0.0136916638 H 12.4307334794 4.6347522320-0.6790931422 12.3878425468 1.8428402020 3.4839700438 H 11.9755110194 1.5147883210 4.4301311544 12.5941257516 3.5553144531 1.8128105665 16.4030152892-0.5736148016 3.0342800265 H 15.4283454867-0.5180388750 2.9936400031 18.8521833314 3.3075209456-0.0776926443 H 19.5422382349 3.7856003273 0.4223444698 20.6132357380 4.8602837657 1.4587605742 20.1540782224 3.8111575794 6.8843406107 18.6630130892 8.3059137544 4.5727025387 15.9765355142 5.9101154899 8.7936689903 13.4129824170 8.4080523147 4.6793230093 12.1285639694 3.2934124124 6.3997649510 12.2120522017 4.8064083639 1.3907021503 13.6197060697-0.2498674751 3.1777426876 Figure S28. Side view (left) and top view (right) of the DFT optimized structure for 1. S29
onformer 1 a2 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*]= -2418.2898562 Hartrees (oordinates in Ångströms) atom x y z 14.8958846263 0.5093053302 1.0725507187 H 14.8072628350 0.5884380597-0.0166372834 H 14.6389550311-0.5246451980 1.3274034524 16.3417810643 0.8063336514 1.4534147000 16.8867348657 0.4119114113 2.6920982630 18.2107010991 0.7308052650 2.9989322711 H 18.5964868837 0.4202170474 3.9662104917 19.0287022809 1.4502206363 2.1234127344 18.4840948189 1.8299951015 0.8876337590 17.1670718863 1.5039769269 0.5680037991 H 16.7884636753 1.8089536935-0.4043479712 20.4299378025 1.8517254946 2.5594221344 H 20.8487425468 1.0638522104 3.1885093773 H 21.1128823534 1.9162082592 1.6962476312 20.4543223492 3.1644878198 3.3362690939 19.8409439961 4.3108447165 2.8173489399 H 19.3818739158 4.2509808351 1.8371938367 19.7810559979 5.4991755653 3.5443775509 20.3338684139 5.5692535794 4.8359513679 20.9783538977 4.4378205690 5.3376062980 H 21.4174371762 4.4962122517 6.3282377830 21.0481089812 3.2447816129 4.6042523448 18.5041979411 6.6028916605 1.8512504180 H 19.1840378957 6.3812505687 1.0168983583 H 18.0766208686 7.5979373716 1.7105679391 H 17.6981775431 5.8570436547 1.8612246467 22.2554767864 2.1276069964 6.3505762763 H 23.0598437977 2.8733405094 6.4155743744 H 22.6766833958 1.1318075120 6.5065248577 H 21.5152788672 2.3328532792 7.1365237474 20.1641035865 6.8248156732 5.6695357649 H 20.4704943821 7.7020659096 5.0957789757 H 20.8271251743 6.7631145198 6.5430007554 18.7238922153 7.0258468720 6.1325477815 18.0431858963 5.9964229445 6.7895157290 H 18.5711829140 5.0646103867 6.9596377065 16.7125474945 6.1326944629 7.1897712077 16.0101935490 7.3194956833 6.9193344740 16.6975656750 8.3567012631 6.2860527400 H 16.1526558059 9.2691659729 6.0750652949 18.0373760525 8.2276192259 5.9017290036 16.6341640524 3.8942772097 8.0355710844 H 16.9133861417 3.4386109757 7.0764881711 H 15.8959267697 3.2612257975 8.5336126041 H 17.5276117558 3.9678557205 8.6711517884 18.0789640212 10.4327314198 4.9677639000 H 17.2330926678 10.2589823356 4.2875983155 H 18.8167678196 11.0659930664 4.4692940127 H 17.7103369199 10.9485182256 5.8656925143 14.5395829315 7.4623443865 7.2859332748 H 14.3851784807 7.1149157451 8.3127733115 H 14.2751138831 8.5245888364 7.2567497128 13.6085869678 6.6830890251 6.3683695300 13.0477355787 5.4710908995 6.7774557793 H 13.2833554354 5.1169747354 7.7735983631 12.2423202216 4.7110117401 5.9251243346 11.9810157342 5.1532805470 4.6188017061 12.5106792777 6.3840163684 4.2209171568 H 12.3059102193 6.7191021722 3.2113493448 13.3082259844 7.1473730858 5.0772664385 S30
13.5940011795 8.8645462537 3.4348501384 H 13.9890389473 8.1922357795 2.6609119921 H 14.1109136665 9.8253099385 3.3744021355 H 12.5211297518 9.0212015706 3.2557867520 11.8528056001 3.0590246553 7.6174919975 H 11.4623759597 3.7829295399 8.3456295132 H 12.9101015646 2.8634025662 7.8437195171 H 11.2888194347 2.1267734887 7.7015174718 11.1936546889 4.2937093215 3.6401684889 H 10.4077650690 3.7541997735 4.1768200821 H 10.7101966415 4.9391272744 2.9014355141 12.0891109832 3.2896992570 2.9287287721 13.1658335755 1.1084620223 2.8606758390 13.8848600579 1.4558302360 1.7105165464 13.6706623585 2.7276040233 1.1694276323 H 14.2247133513 3.0007647832 0.2779785983 12.7070334214-0.5745535861 4.5326946870 H 12.9391408742 0.0733790554 5.3869140686 H 13.0484498529-1.5903096205 4.7416579911 H 11.6233953016-0.5797704445 4.3631100066 13.2169839700 5.2854951143 0.0742199125 H 14.3075785418 5.2942800714 0.2045580991 H 12.8719431510 6.2983118383-0.1457175535 H 12.9628577163 4.6277105046-0.7680207500 12.2836711395 2.0122633311 3.4555164682 H 11.7540585075 1.7540750603 4.3641236720 12.7900558926 3.6369013066 1.7592783002 16.1964484497-0.2977774519 3.6349275216 H 15.2402624026-0.3177288388 3.4343408028 19.1819400901 2.5617966597-0.0562426891 H 20.1144282999 2.5972006723 0.2047015330 21.6650202206 2.1037035574 5.0653742424 19.1883373728 6.6472341840 3.0898696165 18.7497505966 9.2312297121 5.2880912073 16.0125494467 5.1532218336 7.8553028696 13.8421854245 8.3678353939 4.7355233566 11.6739220787 3.5068581255 6.2866914602 12.5507046449 4.8956259160 1.2615697266 13.4035783670-0.1635403967 3.3631957053 Figure S29. Side view (left) and top view (right) of the DFT optimized structure for 1 a2. S31
onformer 1 b1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.2879705 Hartrees (oordinates in Ångströms) atom x y z 14.9187101677 0.1898737620 1.3383186357 H 14.7005412709-0.0101501728 0.2777816981 H 14.7607505568-0.7601064360 1.8523697048 16.3648045628 0.6263494369 1.5298791802 17.0634940209 1.3538496267 0.5543606221 18.3563764536 1.8070481447 0.8079224824 H 18.8650509792 2.3624638241 0.0239887430 18.9999592927 1.5637949438 2.0239209108 18.3121976110 0.8131992189 2.9978029248 17.0181680546 0.3589264756 2.7363027836 H 16.5034251038-0.1981242821 3.5140889738 20.4031013719 3.3207473168 3.2197503627 19.9816303627 4.5763626189 2.7693907667 H 19.6714898772 4.6690475326 1.7341448930 19.9309151413 5.6794249688 3.6220745143 20.3101352835 5.5525206370 4.9723164759 20.7532324321 4.3060013120 5.4159126413 H 21.0527421668 4.2065710571 6.4541636044 20.7926578825 3.2013346456 4.5582084527 19.0419917087 7.1045028804 1.9198353018 H 19.8235510962 6.9050247088 1.1736089200 H 18.7397322821 8.1514520177 1.8508871613 H 18.1763051000 6.4609621780 1.7135648456 21.6203911096 1.7482664790 6.3012596022 H 22.4995214988 2.3690299191 6.5143560522 H 21.8905220198 0.6939534957 6.3865724276 H 20.8272781638 1.9803956338 7.0234219852 20.1602013490 6.7257419314 5.9230464948 H 20.5759219633 7.6300673997 5.4744527113 H 20.7367073866 6.5182998391 6.8342124452 18.7013552579 6.9820628985 6.2888265509 17.9398596239 5.9682690869 6.8784772076 H 18.4211919860 5.0162755801 7.0740627732 16.5902694882 6.1459636297 7.1855166993 15.9506539855 7.3601722939 6.8816237304 16.7170951984 8.3806336514 6.3171154111 H 16.2196882163 9.3136707219 6.0794192608 18.0771232247 8.2114689478 6.0298496414 16.3551948490 3.8917761600 7.9545970343 H 16.6728720055 3.4605092556 6.9963340681 H 15.5541335539 3.2804539126 8.3763905912 H 17.2070332469 3.8918819696 8.6491840192 18.2687175130 10.4411036077 5.1770498505 H 17.4646520641 10.3334732269 4.4352505204 H 19.0643388863 11.0608814858 4.7566685688 H 17.8611747389 10.9354853666 6.0701322093 14.4630707940 7.5512838227 7.1436910161 H 14.2351765015 7.2660382973 8.1770494754 H 14.2292020505 8.6168401691 7.0422461304 13.5682183384 6.7441022528 6.2144187537 12.8866710873 5.6161177727 6.6765676899 H 13.0041120801 5.3467155529 7.7194713189 12.1096078881 4.8271015239 5.8239650087 12.0035721940 5.1504185303 4.4623004317 12.6559866014 6.2994770695 4.0056552490 H 12.5720837682 6.5417076373 2.9529203590 13.4207981950 7.0956399516 4.8624879058 13.9979412045 8.6081527648 3.1003082336 H 14.4235414592 7.8308888025 2.4510896629 H 14.5888943611 9.5220677023 3.0023707208 H 12.9659174962 8.8112907796 2.7818898267 S32
11.4197105602 3.3987970170 7.6213910853 H 11.0104773077 4.2263274516 8.2168549679 H 12.4258519086 3.1589424798 7.9928305829 H 10.7772755188 2.5222276727 7.7352091132 11.2516015118 4.2497559724 3.4930635865 H 10.4213653047 3.7665165936 4.0157278968 H 10.8300319982 4.8585166135 2.6884829494 12.1547532854 3.1794962620 2.8953643073 13.2146605718 0.9867603278 3.0566258979 13.9239241947 1.2148769131 1.8678047783 13.7303524915 2.4310140381 1.2048100453 H 14.3015996177 2.6202184513 0.3029225280 12.7402973579-0.4963366973 4.8786136815 H 12.9789514307 0.2301807562 5.6670530680 H 13.0661592834-1.4902648700 5.1937354931 H 11.6531592018-0.5051282720 4.7196985929 13.3274234469 4.8783786211-0.1294358637 H 14.4181188950 4.8688977020-0.0011202242 H 13.0089137323 5.8746298706-0.4450493046 H 13.0553899830 4.1509163169-0.9064514539 12.3413967014 1.9609213610 3.5512182962 H 11.8066755886 1.8025249005 4.4799519839 12.8635540017 3.4059017619 1.7030367992 16.5243752733 1.6874642998-0.6770796502 H 15.7569811207 1.1195878994-0.8418123238 18.8410901659 0.4825918233 4.2156991197 H 19.7082022930 0.9076750844 4.3569150605 21.1785036528 1.9308903341 4.9631777784 19.5203061055 6.9267445006 3.2400123099 18.8659529626 9.1990422281 5.4885696534 15.8119732159 5.1883116234 7.7892073727 14.0647844552 8.2436834920 4.4651870970 11.4266498949 3.7024029625 6.2396333146 12.6521483854 4.6200568355 1.0882126099 13.4416880550-0.2187519817 3.6811395253 20.3931545487 2.1260313209 2.2729311759 H 20.8119271298 2.4392624461 1.3100361616 H 21.0615442468 1.3487885460 2.6588444672 Figure S30. Side view (left) and top view (right) of the DFT optimized structure for 1 b1. S33
onformer 1 b6 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.2901265 Hartrees (oordinates in Ångströms) atom x y z 15.3731828046 1.8080647291 0.6536314672 16.2379101293 2.7802183555 0.1181128222 17.5717892100 2.8241345410 0.5232641104 H 18.2056711367 3.5948806874 0.0920584974 18.0922240668 1.9352749716 1.4670854114 17.2238825375 0.9698551229 2.0111634553 15.8933498935 0.9179469852 1.5954787529 H 15.2525864087 0.1644433024 2.0463378521 19.5464503928 2.0628664574 1.9132002068 H 19.9076593473 1.0988315431 2.2877890013 H 20.1615989584 2.3039929115 1.0390758381 19.7547333635 3.1506563329 2.9590449251 20.2061327619 4.4178558083 2.5836204385 H 20.4650443210 4.5769773901 1.5424862597 20.3106960136 5.4713038316 3.5011589407 19.9375209993 5.2754953579 4.8403418586 19.5261664360 3.9966242909 5.2250508332 H 19.2407830005 3.8434852360 6.2599189731 19.4454036831 2.9473226945 4.3122672752 21.1102729672 6.9768256316 1.8191814994 H 21.9349760203 6.3356941258 1.4779580078 H 21.4313265556 8.0202563751 1.7853228740 H 20.2514981609 6.8405658415 1.1474855536 18.5751587787 1.4410494798 5.9871247015 H 19.3637217804 1.5989663619 6.7335946099 H 18.2533482289 0.3980558650 6.0146437411 H 17.7220063317 2.0925513531 6.2134466571 18.5513939570 6.6917050200 6.4119794658 18.1578332359 6.2088756768 7.6617137545 H 18.8903109533 5.6730808656 8.2571012394 16.8558436495 6.3934089230 8.1456927326 15.9137614708 7.0979450704 7.3826783902 16.3145221005 7.6036172617 6.1416610096 H 15.5810240955 8.1496403045 5.5579182239 17.6065832091 7.4061592560 5.6521515320 17.3582418647 5.2764677669 10.2094583583 H 17.7756707588 4.3630219113 9.7623001504 H 16.8120142467 5.0109593148 11.1174742170 H 18.1836134943 5.9535937886 10.4690288668 17.1367651767 8.5719001595 3.6168878691 H 16.2734417213 7.9489774699 3.3443991240 H 17.6914530660 8.8345588360 2.7134425751 H 16.7748241181 9.4905712635 4.0993026334 13.4744781140 6.5004327302 7.0451936241 13.4592198302 5.1037571706 7.1285034206 H 14.1684504896 4.6297834764 7.7987826004 12.5749865494 4.3341942106 6.3715001110 11.6616789302 4.9560742031 5.4998574626 11.6618322282 6.3509048134 5.4342291923 H 10.9470024441 6.8317038779 4.7739085963 12.5586355079 7.1237130149 6.1853679254 11.6237809111 9.1778933669 5.3718126550 H 11.6865859732 8.9389196005 4.3006304491 H 11.8177559463 10.2439041953 5.5107903996 H 10.6110999703 8.9449046347 5.7286099906 13.4441819716 2.2769276195 7.2289397032 H 13.3171972658 2.5331297030 8.2900802055 H 14.4817524755 2.4847573965 6.9332455489 H 13.2351504267 1.2142575435 7.0880777607 11.4709164264 3.4887970485 3.4467128845 S34
12.8920568086 3.7510189884 1.4845524861 12.9856938406 2.3609328768 1.3216946314 12.2636790688 1.5564786934 2.2058128249 H 12.3190884633 0.4810968567 2.0758245155 13.7165156979 5.9166087706 0.8081864958 H 12.7535567109 6.4392296666 0.7453168919 H 14.3843425338 6.2911807186 0.0297513476 H 14.1659008282 6.0958731683 1.7926252838 10.8087973638-0.0693970377 3.9928143758 H 10.4167608947-0.3962099650 3.0195845397 H 10.1692314645-0.4624625203 4.7862119238 H 11.8256848247-0.4660926851 4.1185881198 12.1578392268 4.2956965326 2.5356742512 H 12.1301700868 5.3696740327 2.6840629902 11.5050251111 2.0991073808 3.2512261820 15.8279465968 3.6993625029-0.8197169233 H 14.9127639615 3.9490666714-0.5910300395 17.6335356946 0.0399015328 2.9361721546 H 18.3017000079 0.4670523125 3.5057452078 19.0608038778 1.6650546705 4.6707797276 20.7675497059 6.7199324939 3.1674049871 18.0475111352 7.8705026187 4.4403238436 16.4178489916 5.8993875096 9.3561688630 12.6123514130 8.4999098286 6.1229549511 12.5201643394 2.9654916567 6.4087810141 10.7738898677 1.3385135097 4.1273692297 13.5673277147 4.5258074579 0.5566637426 19.9389647332 6.4112179594 5.8589777892 H 20.3443808746 7.3086786004 5.3885516471 H 20.6032976884 6.1493969674 6.6928215060 14.4824423594 7.2989076038 7.8596841106 H 14.2265116846 8.3598585731 7.8007285114 H 14.4127768999 7.0052063693 8.9102613702 13.8971088432 1.7377008949 0.2734015654 H 13.7412913066 2.2111085632-0.7023785763 H 13.6132551114 0.6862122605 0.1524970487 10.7402875609 4.1224166745 4.6261951914 H 9.9338793861 4.7662334029 4.2522328116 H 10.2752815840 3.3316163098 5.2178316714 Figure S31. Side view (left) and top view (right) of the DFT optimized structure of 1 b6 * S35
onformer 1 a3 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.2934662 Hartrees (oordinates in Ångströms) atom x y z 14.3061722294 1.6022014305-0.3855142238 H 14.9876428980 0.9156076532 0.1270557279 H 14.9334559319 2.2505961895-1.0071945364 13.3539958591 0.8414752681-1.2987002426 12.6490163725-0.2956921509-0.8604892011 11.7515820606-0.9246703418-1.7249563238 H 11.2332156947-1.8067144592-1.3570978404 11.5066727189-0.4593162813-3.0203358982 12.2081024092 0.6805684384-3.4558828974 13.1190309137 1.2987674254-2.5975448822 H 13.6506012321 2.1705295818-2.9711377494 10.4892741619-1.1715104612-3.9075942374 H 10.8106177872-1.1313780938-4.9538856653 H 10.4706270865-2.2308353260-3.6287020822 9.0770450180-0.6137307469-3.7771317659 8.2159885820-1.1006467013-2.7887550533 H 8.5641895253-1.9192322403-2.1683632983 6.9484833042-0.5504720622-2.5819904468 6.5150016015 0.5422817400-3.3534723762 7.3542941561 0.9972069565-4.3707715202 H 7.0194115870 1.8369593080-4.9681010915 8.6077099787 0.4239803509-4.5924667417 6.4780803648-2.0478633289-0.7744378834 H 6.7077938133-2.9729809395-1.3208955750 H 5.6384995349-2.2305029079-0.0999535277 H 7.3573247317-1.7517893609-0.1865009965 9.0338963916 1.8754393099-6.4782504409 H 8.1219809466 1.5834129981-7.0131998244 H 9.8463082144 2.0184459418-7.1934506267 H 8.8544616688 2.8135506725-5.9380961578 5.2118150060 2.0128393183-1.7486177286 4.4799121522 1.5681952392-0.6464428013 H 3.8766646070 0.6758226695-0.7658496620 4.5454671353 2.2168281769 0.5909010374 5.3844188560 3.3292966939 0.7602551260 6.0870587574 3.7984954041-0.3534147938 H 6.7359766751 4.6575337251-0.2213152463 5.9976709888 3.1670635308-1.5966864883 3.0114082434 0.6703082390 1.5870010277 H 2.2217166609 0.8041539962 0.8343381934 H 2.5514177792 0.5344475507 2.5686128497 H 3.5929723502-0.2274426568 1.3336371371 7.5736863643 4.6677912101-2.5949496925 H 7.0794300298 5.5995818933-2.2864144352 H 8.0143653772 4.8094155553-3.5848067204 H 8.3687943455 4.4300173189-1.8755553422 5.5433791012 3.9979667790 2.1215745881 H 5.0203577719 4.9640962644 2.1236429321 H 5.0487749971 3.3723208143 2.8689128049 6.9901367313 4.2270477029 2.5158540717 7.5145070090 5.5126921640 2.6623797604 H 6.8479884290 6.3560175954 2.5136987726 8.8624119382 5.7280945570 2.9827322425 9.7281782020 4.6364984412 3.1430390291 9.1967732718 3.3487682872 3.0196471410 H 9.8683310441 2.5053742780 3.1354135881 7.8509026588 3.1344543876 2.7241640402 8.1247279206 0.7596607393 2.6357511916 H 8.8927122133 0.8070815212 1.8524105001 H 7.4764695685-0.1005476411 2.4553039136 H 8.6153523076 0.6393924566 3.6119641230 S36
8.5870023675 8.1086386279 2.9632999962 H 7.7504778125 8.1266679653 3.6758696452 H 8.1840227831 8.1568967591 1.9417555085 H 9.2245492302 8.9784213618 3.1381235566 12.0930273428 4.0338755995 2.4807023171 13.4352524977 2.0640005319 1.9753517948 13.5800287279 2.4625712078 0.6416720539 12.9894407566 3.6688340087 0.2504943017 H 13.0957872881 3.9750133936-0.7844979519 13.9475884040 0.4105906669 3.6600008301 H 14.4173849789 1.1316874113 4.3403440431 H 14.4946341967-0.5334153872 3.6968447558 H 12.9083904602 0.2412634226 3.9696566821 11.7532976786 6.0876375118-0.5222223793 H 12.7973389809 6.2690319534-0.8125929558 H 11.2017988619 7.0294054028-0.5590955019 H 11.3054167160 5.3751371083-1.2284192128 12.7065661299 2.8453283011 2.8791069900 H 12.5900814501 2.5280007962 3.9102332178 12.2572530087 4.4491209314 1.1453149401 12.7942433751-0.8526166195 0.3836408558 H 13.3439060166-0.2904165034 0.9614863245 12.0765185599 1.2193809403-4.7099936375 H 11.1978921687 0.9950561436-5.0751143736 9.4637648327 0.8427637108-5.6020982286 6.0602958569-1.0133177640-1.6452646905 6.6520753551 3.6020382593-2.7257677232 3.8327646957 1.8150077627 1.6963235068 7.2792989650 1.8943369098 2.6089229359 9.4128185493 6.9768008296 3.1499997332 11.6528163988 5.6318666830 0.8141066501 14.0256039934 0.8541471979 2.3123567013 5.1950048621 1.2398781194-3.0600060014 H 4.3873829163 0.5005595421-3.0177772818 H 4.9707541946 1.9194945951-3.8899371481 11.2154661946 4.8291472462 3.4275336107 H 11.4354833540 4.5192993049 4.4576270944 H 11.4510174627 5.8926585375 3.3552843420 Figure S32. Side view (left) and top view (right) of DFT optimized structure 1 a3 *. S37
Transition state in the conversion of conformer 1 to 1 a2 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.282012 Hartrees (oordinates in Ångströms) atom x y z 21.1377850873-2.8921428112 4.7065440764 H 20.1954773514-3.4450204370 4.7888455775 H 21.8568569425-3.5672929907 4.2319413781 20.9073316764-1.6501029694 3.8532185641 21.9545297647-1.0212598900 3.1549163037 21.7304962398 0.2065841325 2.5287096928 H 22.5728759978 0.6850677560 2.0359781489 20.4989378963 0.8550426781 2.5956689595 19.4434695372 0.2035066391 3.2525011918 19.6525375905-1.0304148892 3.8580013817 H 18.8200727716-1.4871970811 4.3873310543 20.3452725965 2.2706415051 2.0798615206 H 21.0685361093 2.4204534526 1.2680397587 H 19.3588102028 2.3851668516 1.6045958335 20.5368523447 3.4270277642 3.0801109688 20.4598864521 4.7320112222 2.5610398734 H 20.2424045855 4.8412744554 1.5026555908 20.6704970120 5.8667202671 3.3455022529 20.9807049148 5.7315928974 4.7112728573 21.0399431606 4.4442899368 5.2298859840 H 21.2764876929 4.3256089207 6.2776520068 20.8187241759 3.2998205114 4.4518639426 20.3087642145 7.3616699407 1.5088004295 H 21.0630822389 6.9070985735 0.8513950973 H 20.3064125763 8.4436318124 1.3580926245 H 19.3203279384 6.9587119653 1.2476179998 21.2191102397 1.8947291695 6.3639168375 H 22.2183973542 2.2953216012 6.5786621117 H 21.2142698747 0.8193945522 6.5472895235 H 20.4929946419 2.3815599174 7.0292728141 21.2474515950 6.9657030987 5.5744189051 H 20.3307256488 7.5621483604 5.6382781253 H 21.9830948121 7.5979011768 5.0619047578 21.7464048035 6.6088378474 6.9579071542 23.1114027480 6.4192711584 7.1895913695 H 23.8004396776 6.6564985780 6.3856136986 23.5856455583 5.8791657489 8.3889027373 22.6830362505 5.5002189391 9.3963356799 21.3222072748 5.7475291193 9.1914264443 H 20.6322559400 5.4520085148 9.9735305164 20.8509168645 6.3021820668 7.9970617301 25.8718162073 6.1154397675 7.7052959865 H 25.7841100026 5.5941851345 6.7421482100 H 26.8520652652 5.9043992770 8.1389633941 H 25.7763462542 7.1963480734 7.5352277898 18.5742693970 6.2204006667 8.7343873170 H 18.5769437484 5.1490967893 8.9782431013 H 17.6007901394 6.4924773398 8.3203700021 H 18.7502396394 6.7953576316 9.6540334321 23.1547032432 4.7698730530 10.6451118773 H 24.1862837374 5.0576967818 10.8650433667 H 22.5368711881 5.0704102528 11.4952949324 23.0829074305 3.2548861658 10.4883658986 24.1239551788 2.5524796538 9.8720055566 H 24.9754471075 3.1227693683 9.5188876566 24.0738945113 1.1652938868 9.7037490005 22.9637441157 0.4341048787 10.1597172699 21.9225719060 1.1368879275 10.7720582442 H 21.0638661074 0.5709024136 11.1129667384 21.9686706577 2.5256633954 10.9342829334 19.8701976062 2.5511426793 12.0947629535 S38
H 19.2988225159 1.9996419698 11.3352784773 H 19.2262402073 3.3081783403 12.5483968748 H 20.2022478757 1.8471523995 12.8699002072 26.2256590348 1.1211925579 8.6521644762 H 26.7464131075 1.6418856335 9.4671939116 H 25.9701461884 1.8486404307 7.8699846644 H 26.8875866187 0.3597009925 8.2330205394 22.9119473069-1.0826027187 10.0237703221 H 23.9082073512-1.4881034229 10.2268922992 H 22.2376045265-1.4740967466 10.7912828833 22.4549107059-1.5913905286 8.6639281977 22.9723478566-2.4511663937 6.4425874876 21.6131201388-2.5196024556 6.1087949417 20.6864583555-2.1467887094 7.0883713613 H 19.6328209588-2.2015810928 6.8379594868 25.2559039128-2.7743664792 5.7247797229 H 25.5659330262-1.7445285258 5.9412966421 H 25.7540415668-3.1215119534 4.8174607972 H 25.5324157291-3.4233544012 6.5647061187 18.8210787735-1.3763959098 9.0577800801 H 18.5466969796-0.7155025670 8.2248682079 H 18.3177356551-1.0391763197 9.9665726727 H 18.4961253800-2.3994809596 8.8255366934 23.3798532962-1.9926288330 7.6977673586 H 24.4321289034-1.9160832024 7.9429147262 21.0878252882-1.6889006189 8.3466305987 23.2177189858-1.5466386724 3.0523779442 H 23.3977495227-2.1282503270 3.8159252918 18.1843538797 0.7594457798 3.3667297264 H 18.2715981356 1.7245914284 3.3483033590 20.8697584835 2.0477152808 4.9979403314 20.6124389457 7.1576082499 2.8754224976 19.5236173823 6.5321057583 7.7322355308 24.9203881276 5.6501589943 8.6458410663 20.9591449486 3.2544792777 11.5259755920 25.0803334817 0.4308233281 9.1186467700 20.2096228799-1.3184042866 9.3361858735 23.8619821989-2.8520728850 5.4570059852 Figure S33. Side view (left) and top view (right) of the optimized transition state between conformers 1 and 1 a2. S39
Transition state in the conversion of conformer 1 a2 conformer 1 b1 Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*]= -2418.275132 Hartrees (oordinates in Ångströms) atom x y z 14.8477795804 1.1990494222 0.3202883904 H 14.8233898142 1.6244018755-0.6947337874 H 14.5649893137 0.1421322274 0.2288160497 16.2730750993 1.3197853385 0.8629226842 17.3735243129 0.9787052770 0.0547840909 18.6705004339 1.1803549466 0.5138966439 H 19.4886637944 0.9377632408-0.1605602294 18.9538500240 1.7035307042 1.7866184418 17.8513907306 1.9638916425 2.6224056539 16.5480498305 1.7878657652 2.1428673434 H 15.7388697003 2.0559489574 2.8132049675 20.4391366060 1.9370758931 2.1140474390 H 20.9615389702 0.9753697906 2.0810164287 H 20.8589780967 2.5340476628 1.2931576393 20.7552328497 2.6408254771 3.4184661844 20.6016458742 4.0332223911 3.5112270935 H 20.3357121566 4.5737105965 2.6087639067 20.6924443689 4.7014751411 4.7321064035 20.9489272128 3.9768724080 5.9123012201 21.2151787717 2.6105864303 5.8043377073 H 21.4442265006 2.0603893589 6.7110924322 21.1263684839 1.9362971319 4.5763021967 20.0635052970 6.7991638233 3.7736195007 H 20.8120249640 6.8076942245 2.9693424012 H 19.9213413949 7.8177631720 4.1397909032 H 19.1127992014 6.4178845623 3.3780754562 21.7412909941-0.1629014074 5.5552491786 H 22.6810782514 0.2203660902 5.9753477926 H 21.8956290234-1.1819117647 5.1946855157 H 20.9740952006-0.1717671537 6.3416633355 20.7944077388 4.6491312951 7.2629772021 H 21.2893206365 5.6215726330 7.2695928216 H 21.2737092171 4.0282674996 8.0308294056 19.3159705275 4.8416221995 7.6044316733 18.4520574802 3.7425849697 7.6354319311 H 18.8607255702 2.7588489161 7.4294426181 17.0883585796 3.8803507548 7.9019430326 16.5424074047 5.1501336257 8.1492922700 17.4058536446 6.2478555525 8.1324343804 H 16.9810107791 7.2287105966 8.3137013347 18.7745055407 6.1100393798 7.8692415709 16.5827547091 1.6162302778 7.3099557163 H 16.9116529244 1.8120361247 6.2822595932 H 15.6811907735 0.9984917291 7.2952943076 H 17.3719794969 1.0720193442 7.8489544469 19.1432068261 8.4701849398 8.0516365246 H 18.4021123862 8.7376444151 7.2850223002 H 19.9997627239 9.1443237345 7.9743551380 H 18.6833459566 8.5857805458 9.0432802947 15.0624032186 5.3212583177 8.4634913162 H 14.7986539562 4.6609864735 9.2981041697 H 14.9077199663 6.3493586430 8.8091408615 14.1036090981 5.0353869063 7.3169663575 13.2941315776 3.8973443609 7.3276889238 H 13.3935989857 3.2150218522 8.1637370116 12.4041436535 3.6182884734 6.2867754000 12.3014793134 4.4897599077 5.1908562860 13.0965112171 5.6403400128 5.1880434356 H 13.0196034831 6.3050315493 4.3353457927 13.9826752880 5.9195148109 6.2328100097 14.7584597988 7.9225419132 5.1783445193 S40
H 15.0619680197 7.4109031418 4.2548229779 H 15.4806794441 8.7096026275 5.4083299607 H 13.7692578406 8.3763722693 5.0245291246 11.6293033844 1.6197810170 7.3624004208 H 11.3452317355 2.1237631479 8.2964184238 H 12.6233236904 1.1688407345 7.4908477855 H 10.9027407557 0.8329799310 7.1450752972 11.4030021173 4.1620893089 4.0045563261 H 10.5451404039 3.5776887617 4.3482695292 H 11.0228753679 5.0899215694 3.5693740383 12.1620771846 3.3751429512 2.9456197557 13.1009106663 1.2593649560 2.1703618620 13.8187593509 1.9210794643 1.1634497960 13.6484032436 3.3021959034 1.0275205653 H 14.2054512224 3.8085711202 0.2462494479 12.6431537500-0.8049008781 3.2950497763 H 12.9642036137-0.4409810155 4.2804134192 H 12.9419705085-1.8492770538 3.1807519436 H 11.5487068674-0.7327501298 3.2281636769 13.3178353411 6.0929567356 0.7798608441 H 14.4097479372 6.0038273949 0.8619816043 H 13.0313888102 7.1409973265 0.8936573995 H 13.0059996188 5.7406235243-0.2130465423 12.2881001700 1.9872816554 3.0461946680 H 11.7730118624 1.4923209494 3.8607210456 12.8327777506 4.0289123386 1.8971927370 17.2300627659 0.4772753030-1.2225307376 H 16.3002167260 0.2499185864-1.3674646019 17.9137080511 2.4123806778 3.9199585328 H 18.8378453864 2.5777709877 4.1616113081 21.3280460793 0.5887296544 4.4278942145 20.5014190156 6.0454507083 4.8899009799 19.6540790573 7.1673189620 7.8553555612 16.2233226958 2.8171212596 7.9800309962 14.7687852704 7.0460581895 6.2881168888 11.5909501797 2.5033434534 6.2577224920 12.6543234140 5.3921805600 1.8152873252 13.2800554062-0.1007509723 2.2452955094 Figure S34. Side view (left) and top view (right) of the optimized transition state between conformers 1 a2 and 1 b1. S41
Transition state in the conversion of conformer 1 b1 conformer 1 b6 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.277289 Hartrees (oordinates in Ångströms) atom x y z 14.6688471892 0.6072227643 0.7066670731 H 15.5142410961 0.4544391697 1.3943195725 H 15.0332651745 1.3270632687-0.0385948041 14.3470425473-0.6900177630-0.0060116285 14.2583803628-1.8935677963 0.7097128855 13.8173760853-3.0520139524 0.0785497998 H 13.7291815947-3.9575154757 0.6737566795 13.4276216118-3.0541373461-1.2654024951 13.5616315719-1.8591284452-1.9971583753 14.0326466391-0.7072854765-1.3638826610 H 14.0813385462 0.2088540442-1.9467849251 11.2123590726-4.1163120573-1.7745981168 10.5520046292-4.2887682447-0.5530957327 H 11.1409614247-4.5920739653 0.3053280032 9.1840963682-4.0468376183-0.4145970459 8.4202490838-3.6250598505-1.5205011367 9.0749501738-3.4757474229-2.7459161835 H 8.4892390931-3.1694623153-3.6065646065 10.4497844513-3.7089588544-2.8758166230 9.2204257057-4.5553632270 1.9235111883 H 9.6928208572-5.5417808144 1.8199057385 H 8.4851764732-4.5925473810 2.7298305268 H 9.9922839598-3.8133473846 2.1680933871 10.4254103858-3.1627018886-5.2281195734 H 9.6641358101-3.9109168706-5.4818265875 H 11.1625364142-3.1072424114-6.0315549467 H 9.9473051142-2.1824503512-5.1055025065 6.9294440192-3.3600097419-1.3781983349 H 6.4680934934-4.1804344150-0.8246080537 H 6.4854141003-3.3558085116-2.3822444810 6.5713006074-2.0494294458-0.6800667803 6.9130143697-0.8208295000-1.2559501835 H 7.4561943896-0.8323017047-2.1951824896 6.5784093614 0.3955453259-0.6534106975 5.8934040293 0.4138823149 0.5752645083 5.5442358073-0.8120746179 1.1445971957 H 5.0199942807-0.7967295941 2.0926998118 5.8642354865-2.0314406320 0.5334869563 7.5897140263 1.6606981964-2.4203246403 H 8.5728023190 1.1794656746-2.3273107922 H 7.7284078926 2.7180213467-2.6575305092 H 7.0324744317 1.1799342258-3.2364312693 4.8362695180-3.2836164578 2.2981900722 H 5.4301183220-2.8162997538 3.0958110861 H 4.6889815375-4.3400706244 2.5315158127 H 3.8573875719-2.7866477123 2.2481863490 5.5442971551 1.7275657333 1.2681364341 H 5.1776529255 2.4413849832 0.5232941444 H 4.7314477706 1.5434198700 1.9771742954 6.7293525453 2.3460531643 1.9966973741 7.4955806469 3.3467420430 1.3915492939 H 7.1819021442 3.7046680228 0.4187619113 8.6684819050 3.8275725051 1.9794375687 9.1149606882 3.2976903026 3.2018699237 8.3050262451 2.3586314679 3.8466906785 H 8.6460924781 1.9578755711 4.7957050330 7.1219205482 1.8877429689 3.2653995666 6.6448621579 0.4771597843 5.1419034746 H 7.6067846559-0.0537520984 5.1404263112 H 5.8522537868-0.2178237053 5.4288647537 H 6.6905941753 1.2940386672 5.8751317399 S42
9.1129771483 5.3030279806 0.1478654630 H 8.1401389302 5.8126330373 0.1863093443 H 9.0752701823 4.5214250130-0.6234692317 H 9.8882096258 6.0272851293-0.1116543661 10.5143798557 3.5939361241 3.6972484843 H 10.7490919534 4.6569222780 3.5877420235 H 10.5848847463 3.3746529206 4.7715011627 11.5727971010 2.7850269226 2.9433708345 12.1729569892 0.9325924543 1.4525154737 13.5338568106 1.2871737267 1.4961510790 13.8799901421 2.3931899818 2.2942848966 H 14.9275342438 2.6768170343 2.3353410751 10.4180754414-0.3635399788 0.4434708762 H 9.8828294952-0.6682386183 1.3525945488 H 10.3786981335-1.1778144791-0.2808812685 H 9.9259503003 0.5258772811 0.0286864849 14.5727814001 4.6796490736 3.8245433101 H 15.2506201411 3.9221061216 4.2432914339 H 14.5752755013 5.5594098731 4.4729156550 H 14.9314267571 4.9651747972 2.8253925372 11.2321563203 1.6767592057 2.1769343471 H 10.1907592896 1.3903470413 2.1273412902 12.9339689658 3.1361432842 3.0039550980 14.5518295903-1.9777576231 2.0563275247 H 14.4329652215-1.1010483893 2.4531834311 13.2329101963-1.7391429011-3.3236294582 H 12.6521334875-2.4713996906-3.6037358561 11.1454301515-3.5411183982-4.0639271565 8.4983979307-4.1944429402 0.7593845359 5.5095985707-3.2511558185 1.0553008267 6.8694998187 1.6237651567-1.2017229746 6.3029124257 0.9504277382 3.8523796478 9.4793822658 4.7755756244 1.4083658191 13.2338406928 4.2241296121 3.7890106286 11.7959931178-0.1348152616 0.6865483326 12.7293185894-4.2760790816-1.8462894161 H 13.0203137380-5.1584675502-1.2656179844 H 13.0399807723-4.4651428961-2.8787669200 Figure S35. Side view (left) and top view (right) of the optimized transition state between conformers 1 b1 and 1 b6 *. S43
Transition state in the conversion of conformer 1 b6 * conformer 1 a3 * Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.280329 Hartrees (oordinates in Ångströms) atom x y z 5.3585335726 7.8149146108 6.5451808077 5.3546258182 7.6250189374 7.9409337091 5.6634416270 8.6963676581 8.7812641313 H 5.6193723728 8.5242056099 9.8536664873 6.0064127102 9.9577128964 8.2874577789 6.0669377720 10.1295569060 6.8923215013 5.7321031165 9.0670797238 6.0521726359 H 5.7669168508 9.2419933835 4.9801584543 6.2800999025 11.1066811713 9.2482429620 H 5.9928396690 12.0529675070 8.7776337968 H 5.6307263940 10.9855388635 10.1222210802 7.7177985767 11.1996367252 9.7366893839 8.1128297258 10.5336242904 10.8988542063 H 7.3655164209 9.9574838568 11.4335619827 9.4232193783 10.6068867457 11.3843446395 10.3884876773 11.3653802013 10.7007368871 9.9927568780 12.0336740369 9.5397657432 H 10.7330236954 12.6243362487 9.0123203133 8.6863114517 11.9512466185 9.0574979631 8.9864162360 9.0323639109 13.1338519482 H 8.0849800953 9.4988776857 13.5560347740 H 9.5667190136 8.5825847122 13.9425947075 H 8.6840913090 8.2496641926 12.4240664906 9.2115280868 13.3212120472 7.1366467287 H 9.6507436562 14.1487451050 7.7076850181 H 8.6618927669 13.7189856915 6.2815164163 H 10.0127809757 12.6591487328 6.7812802976 12.6836328363 10.4047463295 10.4246764036 13.1168481101 10.6670741782 9.1214650137 H 12.9169290889 11.6475253657 8.7033292167 13.7525950912 9.6916707348 8.3497689731 13.9697674313 8.4095616429 8.8800003500 13.5920291455 8.1663101234 10.2006834633 H 13.7664603213 7.1741106792 10.6033923674 12.9650815029 9.1455340408 10.9788072958 13.8337856835 11.1047645794 6.4196590331 H 12.7471011993 11.2776143184 6.3979522234 H 14.2046478443 11.0230884661 5.3956066216 H 14.3208583830 11.9595571880 6.9117223539 12.6636180799 7.6485060692 12.8220321548 H 12.0676477990 6.9308901188 12.2398745162 H 12.2552124545 7.7189057258 13.8330992936 H 13.7003940772 7.2874966427 12.8798225797 13.3579767474 6.5477807430 7.2835617514 12.0284047668 6.9532211219 7.3340503028 H 11.7800404260 7.8224985216 7.9283637280 11.0085233473 6.2796423135 6.6445627096 11.3198241604 5.1467323475 5.8706710414 12.6636850381 4.7442854149 5.8221794569 H 12.9068345976 3.8767730555 5.2162637675 13.6706140246 5.4184872209 6.5097723413 15.3867704546 3.9555228885 5.7036616730 H 14.8993400415 3.0266133027 6.0337079213 H 16.4673655394 3.8567502065 5.8296058637 H 15.1600148339 4.1164069851 4.6399312868 9.3484533790 7.8043670524 7.5129816095 H 9.8350573537 8.7303546067 7.1749826029 H 9.5996633529 7.6411786917 8.5703353004 H 8.2666804524 7.9103613538 7.4098244945 8.9026573537 4.7531847761 5.0160512791 6.6971402246 4.7663879042 6.0226800958 S44
6.3358349271 5.8969016558 5.2829189988 7.2533144730 6.4019173121 4.3557011332 H 6.9735386127 7.2831972362 3.7894844784 6.0637513842 3.1622310067 7.7153652619 H 6.2787516726 2.2871748717 7.0891379351 H 5.1782220782 2.9659868684 8.3236401349 H 6.9206643433 3.3617112954 8.3720209557 9.2568869644 7.5732098189 2.7402293950 H 8.4242216777 7.5033415166 2.0251871282 H 10.1743889547 7.8090780763 2.1977452148 H 9.0431094016 8.3737278305 3.4618206591 7.9655176272 4.1997444418 5.8827208834 H 8.2694543700 3.3623385768 6.5015808713 8.5228861722 5.8460911921 4.2207056900 5.0141995973 6.4432546582 8.5436687398 H 5.1697938267 5.6944453541 7.9340744863 6.3900072586 11.3222375485 6.2970182679 H 6.9875001013 11.8210916639 6.8877516828 8.2594000117 12.6078257727 7.9136733457 9.8414116064 9.9825766577 12.5269500277 12.5843660464 8.9523540609 12.2811519538 14.1537645916 9.8798389122 7.0502124015 14.9995018496 5.0625631844 6.4953926353 9.7041843817 6.6926792708 6.7046300231 9.4964656208 6.3390732812 3.3936968774 5.7435229041 4.2944663838 6.9173438185 11.8376392748 11.4291649194 11.1659385071 H 11.8916751921 11.2505362747 12.2402109146 H 12.2293637130 12.4345294964 10.9693058914 14.4769650440 7.2869256786 8.0092339182 H 15.0428676743 6.5676062930 8.6143520278 H 15.1842166736 7.6678735312 7.2647830462 5.0634505387 6.6749568957 5.5784040788 H 4.2912281563 6.0138754923 5.9834135052 H 4.6673942803 7.0931187637 4.6465232225 10.3421640677 4.3060946204 5.0366492845 H 10.3904547002 3.2710369858 5.4022215902 H 10.7270329737 4.2834101811 4.0100669357 Figure S36. Side view (left) and top view (right) of the optimized transition state between conformers 1 b6 * and 1 a3 *. S45
Transition state in the conversion of conformer 1 a3 * conformer 1* Energy [B3LYP (solvation)/ 6-311g**++// B3LYP/ 6-31g*] = -2418.28721 Hartrees (oordinates in Ångströms) atom x y z 13.3496761448-0.3866394529 4.4802926796 H 14.2102299006-0.3150706823 5.1529160564 H 13.6520072097-1.0245752135 3.6425635491 12.1715607363-1.0439878431 5.1978315555 11.9598951192-0.8959167932 6.5820550032 10.8472957890-1.4947455490 7.1786151163 H 10.7234074289-1.3676127438 8.2513519836 9.9109963297-2.2349541635 6.4501429790 10.1215636905-2.3782884756 5.0647769414 11.2403858007-1.7906172914 4.4707716941 H 11.3706362884-1.9298878907 3.4005464117 8.7023141964-2.8425447620 7.1541059932 H 8.5745862250-3.8886213969 6.8544828078 H 8.9108630681-2.8560007886 8.2296673139 7.3879765357-2.0988826227 6.9314075919 7.0960974974-0.9355396044 7.6515405881 H 7.8307574116-0.5828742873 8.3673912929 5.9013711449-0.2343430221 7.4632972134 4.9469462954-0.6901473564 6.5344217959 5.2343918852-1.8552310621 5.8209133405 H 4.5094470384-2.1933207418 5.0909193216 6.4329000138-2.5466557853 6.0093908352 6.5271149823 1.4437250023 9.0550209758 H 6.7410339595 0.7560258416 9.8839946841 H 6.0800257953 2.3557409541 9.4567941894 H 7.4659046153 1.6940804344 8.5437739427 5.8535443667-4.1879512107 4.3327760303 H 4.8932682745-4.4552797415 4.7903383557 H 6.3195015132-5.0815002360 3.9130210905 H 5.6844324033-3.4530453819 3.5358817955 3.8590630040 1.1816090219 5.2424008283 4.1502258310 2.4900728847 5.6430722193 H 4.1556123032 2.7044631141 6.7050811316 4.4863062324 3.4814212089 4.7170136479 4.5659822260 3.1730554423 3.3479052152 4.2043720282 1.8855667367 2.9438446911 H 4.2597308405 1.6500514031 1.8862289111 3.8387642731 0.8998489877 3.8670247215 4.8426248623 5.1188498482 6.4251429834 H 3.8694296399 4.9731932780 6.9151008435 H 5.1078485041 6.1780985540 6.4596628623 H 5.6032293685 4.5365538160 6.9642462358 3.4833261121-0.7223495050 2.1376204995 H 2.8016764171-0.0811818995 1.5627496696 H 3.1338203939-1.7560325212 2.0818072689 H 4.4888119153-0.6552817775 1.6996034808 5.1783067231 4.1489370809 2.3680802983 H 4.9511145168 3.8297480932 1.3421502630 H 4.7346277607 5.1440539142 2.4814282515 6.6940272812 4.2818547116 2.5204335670 7.4387634433 3.4181385497 3.3181357801 H 6.9182460895 2.6336422626 3.8500378678 8.8233116661 3.5469238326 3.4756086949 9.5290251329 4.5212463565 2.7480202823 8.7786907864 5.3783575686 1.9300760601 H 9.3137341176 6.1321970520 1.3615288209 7.3896484267 5.2804051348 1.8195184937 7.2455134728 7.1857378478 0.3755123588 H 7.6879218996 7.8889884679 1.0946044810 H 6.4578546767 7.6965782477-0.1827244008 S46
H 8.0221186996 6.8531356484-0.3263733653 8.8710505112 1.6944451524 5.0090359390 H 8.4682188179 0.9564071848 4.3037861693 H 8.0558269657 2.0583829199 5.6493241693 H 9.6317299747 1.2115796276 5.6252093897 11.8589804232 3.4543712320 3.1066058686 13.0970592508 2.1432917715 4.7351046602 12.9804242633 0.9913696070 3.9459010924 12.3988870380 1.1253967804 2.6805322632 H 12.3306279676 0.2436253072 2.0525587645 13.9220059138 3.1301546014 6.7813210953 H 14.4829002410 3.9156995415 6.2601849669 H 14.4932018897 2.7889693149 7.6468530005 H 12.9578615278 3.5322631915 7.1170356639 11.0928210204 1.4039240265 0.1857278775 H 12.0659948412 0.9937019272-0.1185171843 H 10.5640153780 1.7690879566-0.6972117815 H 10.5024881654 0.6072036398 0.6582756969 12.5384182218 3.3527450354 4.3189344215 H 12.5556800778 4.2191839762 4.9713428739 11.8542572446 2.3381366998 2.2536245673 12.8176611488-0.2113957553 7.4058990588 H 13.2499884327 0.5026931626 6.8961836242 9.2953870227-3.0875953032 4.2355643624 H 8.4856577420-3.3731675650 4.7008775180 6.7645330755-3.6964994837 5.3072195347 5.5715241878 0.9035068658 8.1594300151 3.4868297414-0.3842140086 3.5127274178 4.7981813655 4.7733476907 5.0538240189 6.6176655574 6.0997599696 1.0275056427 9.5326576844 2.7546760274 4.3392403827 11.2393842799 2.5213127591 1.0426127323 13.7532604874 1.9891163428 5.9509179583 3.6582434692 0.0824294233 6.2770439327 H 3.3120225971 0.5324689773 7.2117483733 H 2.8874585294-0.6142692565 5.9346172681 11.0538617146 4.6871307310 2.7568602841 H 11.3271434388 5.4976128909 3.4480164063 H 11.3393280274 5.0382454633 1.7576467450 Figure S37. Side view (left) and top view (right) of the optimized transition state between conformers 1 a3 * and 1*. S47
Ground state of 3 Energy [B3LYP (solvation)/ LAV3P**++// B3LYP/ LAVP*] = -2444.22248 Hartrees (oordinates in Ångströms) atom x y z Br -0.1351847572 27.0721436383 11.0063385877 Br 0.1570304922 21.2046372430 7.8383296992 4.7688786131 26.5615332455 11.2361494104 3.5505321476 26.6889001552 10.5660543333 H 2.7282863401 27.2245275398 11.0230957643 3.3404631504 26.1181600903 9.3057539929 4.4166301753 25.4415075641 8.7150895360 5.6331112793 25.2996959800 9.3860981785 H 6.4480214734 24.7420602225 8.9406821212 5.8277047053 25.8364544910 10.6593844867 7.1302607535 25.6105994137 11.4130471622 H 7.9166730505 25.3627764048 10.6929580134 H 7.4230802440 26.5369174565 11.9179993496 5.2330524916 24.1908536577 6.8101501866 H 6.1154948858 24.8211762131 6.6473011673 H 4.8286213241 23.8726076554 5.8473732930 H 5.5167154487 23.3097190018 7.3987318012 7.0205888058 24.4999822617 12.4492075763 6.7789379814 24.7988461450 13.7918471967 H 6.6910048782 25.8422640384 14.0685586568 6.6160033004 23.7926552225 14.7490416949 6.7082924494 22.4423124559 14.3782764752 6.9693313815 22.1419187264 13.0375390603 H 7.0329979485 21.0954770757 12.7596345466 7.1232180297 23.1473178371 12.0795648754 6.4935304307 21.3238709426 15.3877911402 H 6.6574193713 21.7152494153 16.3954357172 H 7.2290675587 20.5338914531 15.2140406975 5.0947447085 20.7302078525 15.3012550760 4.0067719416 21.4049591159 15.8640244341 H 4.2044021347 22.3421945278 16.3727403454 2.7055204407 20.9067385368 15.7622699566 2.4599112047 19.6980178843 15.0875140389 3.5495634258 19.0167577066 14.5402469241 H 3.3527390982 18.0918111387 14.0121685809 4.8508940465 19.5204928275 14.6326280503 1.0441816751 19.1591910008 14.9297492374 H 1.0963885534 18.0798826479 14.7522389688 H 0.4892343422 19.3148402766 15.8605456012 0.2829727102 19.8202786947 13.7898021896-0.6498077234 20.8287208004 14.0357953657-1.3059061843 21.4841924082 12.9910804949-1.0360887569 21.1615450663 11.6537888488-0.1296732748 20.1228686368 11.4107659854 0.5174820156 19.4540944023 12.4517234306-1.6578568363 21.9257876553 10.4853390934 H -1.8669909981 21.2242808878 9.6749494858 H -2.6207873696 22.3496829520 10.7868120708-0.7613956290 23.0422796694 9.9511776631 0.1178650674 22.8829515742 8.8761771301 0.9974714715 23.8831614035 8.4418006837 0.9866362762 25.1429868653 9.0832702517 0.0648832150 25.3211217990 10.1187569423-0.7881598734 24.3092331388 10.5775438481 1.8031459970 22.7660933884 16.9683330388 6.3539067685 25.3924720104 16.5140336709 H 7.3211704203 25.8773005036 16.3222524398 H 6.1741209394 25.3619460852 17.5913769947 H 5.5612866431 25.9823292520 16.0324573933 5.7625710832 17.6183525561 13.4950408092 S48
H 5.3541970291 16.8956085200 14.2149801759 H 6.7526472167 17.2858038278 13.1739049768 H 5.0960599631 17.6625979769 12.6221160077 1.6887469720 18.0349706516 10.9209259252 H 0.7902398120 17.6739356555 10.4024853964 H 2.4116613295 17.2192269913 10.9952934667 H 2.1266797326 18.8587123264 10.3424307160 7.4762374288 21.5514716161 10.3313320515 H 8.2964589322 21.0239280915 10.8374935676 H 7.6792254838 21.5811463929 9.2578938773 H 6.5398832487 21.0049660658 10.5078997373-2.5243658719 22.8925056571 14.5366440332 H -2.9456260953 22.0633730573 15.1176913550 H -3.2612475773 23.6940021794 14.4567769493 H -1.6241465909 23.2696554678 15.0373525000 3.9714381101 27.8418927691 13.0949665260 H 3.6705232459 28.7147759578 12.5000499896 H 4.3760222810 28.1821432286 14.0510419783 H 3.0900526574 27.2127788099 13.2749916375 1.9717174226 26.2209203526 8.6334195448 H 2.0870935476 26.1703473699 7.5461779928 H 1.5436780966 27.2009282886 8.8551398642 1.4022606368 18.4245680280 12.2535908275 5.9483345741 18.8925988515 14.0810551037 7.3822583181 22.9001556026 10.7507295734 4.1939287018 24.9269592013 7.4443190144 1.8007184950 23.6089447232 7.3835545409 H 2.6022421038 24.1734793381 7.3862019997 6.3478155614 24.0466515492 16.0778403310 1.6052377208 21.5339478215 16.3003347840 5.0144208070 27.1157905112 12.4669216762-2.2450796723 22.4861998088 13.2019793604-1.6426696234 24.6068935420 11.5877793495 H -1.9181465886 23.8012413695 12.0734959344 H 2.4625546660 22.6553468349 17.8402311693 H -0.8327816692 21.1104984945 15.0657861655 H 0.0750788608 19.8594175975 10.3808438876 H 2.2244968309 23.5278710089 16.2984654485 H 0.8154702535 23.0898167793 17.3060176101 Figure S38. Side view (left) and top view (right) of the optimized ground state of 3. S49
Assumed highest energy transition state of 3 Energy [B3LYP (solvation)/ LAV3P**++// B3LYP/ LAVP*] = -2444.19174 Hartrees (oordinates in Ångströms) atom x y z Br -0.9658346142 22.4502690131 7.0689119389 Br -2.2309019119 25.5141729351 12.8695252760 0.5135205706 25.6268213903 4.8705125994-0.2099649160 25.9553749323 6.0167951553 H 0.2561095353 26.5242367132 6.8148393643-1.5096174853 25.4821476977 6.2169906653-2.1353248367 24.7819627265 5.1778030356-1.4007944442 24.4256948769 4.0430386779 H -1.8410949969 23.7914600490 3.2826051051-0.0565648319 24.7816852498 3.9014247796 0.8004182373 24.1771980915 2.7997105297 H 0.1498062477 23.7909458654 2.0085054461 H 1.4396459202 24.9471218631 2.3558635337-4.0716275995 23.5737566157 4.4555011527 H -4.1402919037 24.0442242854 3.4647411299 H -5.0802449333 23.3956078120 4.8377428975 H -3.5445105689 22.6152696091 4.3629035782 1.6831602866 23.0599021533 3.3486604554 3.0273399939 23.2989324019 3.6447424630 H 3.4268693193 24.2805667474 3.4219109732 3.8341259214 22.3230331972 4.2376648988 3.3044156504 21.0623484501 4.5584670756 1.9634428102 20.8158174496 4.2464451644 H 1.5593690859 19.8414001520 4.4972234537 1.1589124228 21.7893049128 3.6460671186 4.1637528116 19.9830060309 5.2030545612 H 5.2075790305 20.1552414800 4.9260247183 H 3.8693603788 19.0108827247 4.7985976714 4.0745079572 19.9283124472 6.7236875898 4.8602084646 20.7765741561 7.5080312004 H 5.4928922341 21.4897878814 6.9936579572 4.8269439128 20.7249194289 8.9048591575 4.0137856126 19.7858719644 9.5589530839 3.2176346227 18.9448573551 8.7762908446 H 2.5760006966 18.2338895908 9.2875331238 3.2291581641 19.0166147418 7.3794338136 3.9647616127 19.7016326794 11.0806259375 H 3.9416863047 18.6528770161 11.3860963540 H 4.8717201647 20.1494656394 11.4949987520 2.7426787901 20.4162449339 11.6360094527 2.7082921988 21.8128106007 11.6720723127 1.5462854200 22.5104633378 12.0109666269 0.3635637316 21.8071918298 12.3081761147 0.4249018134 20.4063869992 12.3668491785 1.5957952947 19.7093302090 12.0380430174-0.9662872327 22.5375551421 12.4224758963 H -1.7489156611 21.8072172125 12.6759703064 H -0.9292803506 23.2549638410 13.2456211825-1.3658934388 23.2921124947 11.1503813812-1.8939739613 24.5849199342 11.1673968193-2.2245461739 25.2810688346 10.0012268629-1.9326020086 24.7411881818 8.7244292713-1.4408745343 23.4291645288 8.7059893489-1.2243056076 22.6897485543 9.8807133382 6.3885541496 22.5315319383 9.0978501322 5.7614255067 23.7478130662 4.1601389673 H 5.6994262567 23.9006432757 3.0735705897 H 6.8118870453 23.6788684386 4.4540048482 H 5.3017382710 24.6094791702 4.6644680200 S50
1.6107608701 17.2651877200 7.1858705487 H 2.1832209990 16.5401073462 7.7774904081 H 1.1026672888 16.7428852410 6.3714207694 H 0.8630477018 17.7422538705 7.8331740593 0.5775475650 17.5880204997 12.5018404624 H 0.3058371076 17.8706100687 13.5282065644 H 0.8929614398 16.5425281963 12.4857453768 H -0.3032118600 17.7078256857 11.8541968379-0.7553097738 20.3486970149 3.6575907544 H -0.2716213076 19.5061255513 3.1451137900 H -1.7968956318 20.4141879348 3.3318649014 H -0.7261847005 20.1742517135 4.7412475280 2.5755519810 24.6421369145 11.6483585252 H 3.4317487933 24.4686400960 12.3162544643 H 2.2639422711 25.6853705672 11.7268409281 H 2.8753493566 24.4266875893 10.6132883003 2.3875136831 26.9393653382 5.5627828498 H 1.7812499097 27.8482232812 5.6801524428 H 3.3635405183 27.2067166654 5.1511133789 H 2.5280573896 26.4786589741 6.5502684325-2.1792691042 25.7109585435 7.5523199433 H -3.2625860748 25.8073315000 7.3926965634 H -1.8292072384 26.6969364168 7.8930570736 1.6829826051 18.3383789773 12.0284880837 2.4530683904 18.2183462079 6.5707336051-0.1583983223 21.5846799455 3.3094598962-3.4411184185 24.4217676466 5.3970782590-2.7875852710 26.5186275789 10.1552105514 H -2.9771512430 26.9003447230 9.2873988376 5.1632203374 22.5274977263 4.5527090770 5.5804820397 21.5484511173 9.7150249408 1.8040670488 26.0398468850 4.6410350458 1.4478777765 23.8730153919 12.0346229035-0.8675273319 21.3861972187 9.7311541317 H -0.4025497849 21.0739586146 10.5278039509 H 7.1721850763 22.0792632175 8.4750351592 H 3.6033586688 22.3461606992 11.3698386095 H -0.4806569993 19.8646102019 12.6293052796 H 5.7951645399 23.2166105486 8.4783190559 H 6.8575211000 23.0914908603 9.9112551342 Figure S39. Side view (left) and top view (right) of the highest energy transition state of 3. S51