Supporting Information. DFT Study of Pd(0)-Promoted Intermolecular C H Amination with. O-Benzoyl Hydroxylamines. List of Contents

Supporting Information DFT Study of Pd(0)-Promoted Intermolecular C H Amination with O-Benzoyl Hydroxylamines Yunfei Zhou and Xiaoguang Bao* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China. E-mail: xgbao@suda.edu.cn List of Contents Computational Methods.... 2 References.... 2 Scheme S1.... 3 Cartesian Coordinates and Energies.... 4-38 1

Computational Methods All structures were optimized with the ωb97xd 1 density functional theory method combined with the 6-31G(d) 2 basis set for C, H, O, N, F atoms and LANL2DZ 3 basis set for Pd and Cs atoms. Vibrational analyses were performed on all optimized geometries, to ensure that the optimized structures corresponded to local minima. And further single-point energies were obtained with the 6-311++G(d, p) for C, H, O, N, F atoms and LANL2TZ(f) basis set for Pd and LANL2DZ for Cs. Solvent effect was also considered using SMD 4 model with dichloroethane as the solvent for the single-point energy calculation at larger basis set. The solution-phase Gibbs free energy was determined by adding the solvation single-point energy and the gas-phase thermal correction to the Gibbs free energy obtained from vibrational frequency calculation. Unless otherwise specified, the solution-phase Gibbs free energy was used in the discussion. The Gaussian 09 suite of programs 5 was used throughout. References 1. Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615-6620. 2. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta. 1973, 28, 213-222. 3. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299-310. 4. Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378-6396. 5. Gaussian 09, Revision C.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc., Wallingford CT, 2010. 2

Scheme S1. The energy profile for the formation of the key Pd(IV) intermediate with INT4 intermediate. 3

Cartesian Coordinates and Energies Pd(dba) 2 1 6 0 0.514601-1.896172-0.889412 2 8 0 0.714928-1.880820-2.096401 3 6 0-0.849629-2.053893-0.305607 4 6 0-1.987462-1.887398-1.075407 5 1 0-0.899975-2.444939 0.709329 6 1 0-1.840132-1.682918-2.135715 7 6 0 1.598554-1.728963 0.107259 8 6 0 2.888464-1.751642-0.254284 9 1 0 1.297457-1.564911 1.138770 10 1 0 3.105213-1.946884-1.303760 11 6 0 4.041809-1.511671 0.617860 12 6 0 5.325496-1.799314 0.139862 13 6 0 3.911220-0.943960 1.893953 14 6 0 6.449786-1.542120 0.915653 15 1 0 5.439466-2.213844-0.858082 16 6 0 5.034590-0.683877 2.667858 17 1 0 2.930432-0.663643 2.267051 18 6 0 6.307218-0.983558 2.182493 19 1 0 7.437889-1.764718 0.524402 20 1 0 4.917696-0.233995 3.649407 21 1 0 7.184461-0.772667 2.787209 22 6 0-3.378992-2.112146-0.628453 23 6 0-4.421640-1.554798-1.383865 24 6 0-3.700034-2.788794 0.557056 25 6 0-5.739579-1.644433-0.954771 26 1 0-4.184107-1.023750-2.301861 27 6 0-5.019279-2.882846 0.981964 28 1 0-2.913100-3.248220 1.147590 29 6 0-6.043030-2.305102 0.233097 30 1 0-6.529863-1.190809-1.544935 31 1 0-5.250109-3.411580 1.902086 32 1 0-7.072714-2.378268 0.570313 33 6 0 0.488778 1.866167 0.888923 34 8 0 0.688070 1.816514 2.095260 35 6 0 1.575509 1.728064-0.109263 36 6 0 2.863842 1.747178 0.258186 37 1 0 1.278633 1.586166-1.145318 38 1 0 3.075343 1.924054 1.311931 39 6 0-0.876734 2.036636 0.311154 40 6 0-2.011238 1.828095 1.075292 41 1 0-0.935578 2.467126-0.687530 42 1 0-1.860354 1.574890 2.124646 43 6 0-3.403651 2.081440 0.644720 44 6 0-4.441027 1.402400 1.301636 45 6 0-3.726521 2.919032-0.431228 46 6 0-5.757474 1.535557 0.879919 47 1 0-4.199208 0.739144 2.128019 48 6 0-5.045379 3.057929-0.846464 49 1 0-2.941362 3.472500-0.937927 50 6 0-6.064358 2.362524-0.198025 51 1 0-6.543372 0.985742 1.388544 52 1 0-5.280410 3.715825-1.677996 53 1 0-7.093329 2.471933-0.527417 54 6 0 4.021983 1.524241-0.611955 55 6 0 5.301121 1.825831-0.130427 56 6 0 3.900492 0.955697-1.888458 57 6 0 6.429930 1.582560-0.904050 58 1 0 5.408114 2.240024 0.868432 59 6 0 5.028547 0.709292-2.660155 60 1 0 2.923643 0.663218-2.262616 61 6 0 6.296433 1.023493-2.171745 4

62 1 0 7.414590 1.815854-0.510357 63 1 0 4.919107 0.258192-3.641993 64 1 0 7.177471 0.822856-2.774412 65 46 0-1.636173-0.008144-0.032143 0.526120 (Hartree/Particle) Thermal correction to Energy= 0.559573 Thermal correction to Enthalpy= 0.560517 Thermal correction to Gibbs Free Energy= 0.454161 Sum of electronic and zero-point Energies= -1588.640978 Sum of electronic and thermal Energies= -1588.607525 Sum of electronic and thermal Enthalpies= -1588.606581 Sum of electronic and thermal Free Energies= -1588.712936 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -1589.134965 1a 1 6 0-5.592944 0.655567-1.184880 2 6 0-4.228780 0.431990-1.031696 3 6 0-3.743812-0.158818 0.138130 4 6 0-4.635808-0.539259 1.143165 5 6 0-5.996623-0.308702 0.990423 6 6 0-6.476155 0.290899-0.172490 7 1 0-5.967298 1.105172-2.099190 8 1 0-3.552109 0.684686-1.843253 9 1 0-4.242387-1.015670 2.034962 10 1 0-6.686299-0.600662 1.776151 11 1 0-7.540743 0.466308-0.294047 12 6 0-2.294053-0.441206 0.365191 13 8 0-1.894362-1.280572 1.143386 14 7 0-1.419473 0.344652-0.386379 15 1 0-1.755173 1.252323-0.676292 16 6 0-0.034164 0.229007-0.253142 17 6 0 0.739714 1.360766-0.013155 18 6 0 0.627433-0.990412-0.400303 19 6 0 2.121491 1.297105 0.097306 20 6 0 2.004495-1.057454-0.258209 21 6 0 2.780981 0.074950-0.009901 22 9 0-0.043029-2.091679-0.707686 23 9 0 2.592486-2.241646-0.399280 24 9 0 2.770945 2.434568 0.321590 25 9 0 0.127301 2.544975 0.102330 26 6 0 4.278534-0.094438 0.104154 27 9 0 4.789995-0.567002-1.042286 28 9 0 4.905003 1.050341 0.383489 29 9 0 4.583227-0.969570 1.072030 0.183625 (Hartree/Particle) Thermal correction to Energy= 0.202659 Thermal correction to Enthalpy= 0.203603 Thermal correction to Gibbs Free Energy= 0.134095 Sum of electronic and zero-point Energies= -1365.358320 Sum of electronic and thermal Energies= -1365.339286 Sum of electronic and thermal Enthalpies= -1365.338342 Sum of electronic and thermal Free Energies= -1365.407850 ωb97xd /6-311++G (d, p)/smd//ωb97xd /6-31G(d) energy= -1365.815447 2 1 6 0-2.438468 1.157603 0.514788 2 6 0-2.801136 0.008810 1.449210 3 6 0-2.943777-1.482761-0.337737 4 6 0-2.572310-0.382450-1.330935 5 1 0-1.888229-0.471751 1.834067 5

6 1 0-3.381986 0.375075 2.299648 7 1 0-3.349005 1.677848 0.198615 8 1 0-1.780343 1.887673 0.990278 9 1 0-2.040908-2.026543-0.018686 10 1 0-3.631849-2.196950-0.798050 11 1 0-2.004222-0.779241-2.176479 12 1 0-3.483230 0.085943-1.718433 13 7 0-1.798035 0.707707-0.730396 14 8 0-3.610984-0.942494 0.784576 15 8 0-0.540498 0.090343-0.382338 16 6 0 0.485186 0.967811-0.283337 17 8 0 0.360353 2.166626-0.308215 18 6 0 1.781861 0.253745-0.095450 19 6 0 1.890342-1.138295-0.146881 20 6 0 2.917342 1.033338 0.133265 21 6 0 3.129732-1.742253 0.030526 22 1 0 1.007704-1.741503-0.327207 23 6 0 4.153786 0.425860 0.311525 24 1 0 2.809860 2.112394 0.167031 25 6 0 4.260825-0.962276 0.260421 26 1 0 3.214519-2.823817-0.012206 27 1 0 5.035231 1.033820 0.490418 28 1 0 5.227438-1.437490 0.399216 0.233736 (Hartree/Particle) Thermal correction to Energy= 0.246150 Thermal correction to Enthalpy= 0.247095 Thermal correction to Gibbs Free Energy= 0.192856 Sum of electronic and zero-point Energies= -706.909484 Sum of electronic and thermal Energies= -706.897069 Sum of electronic and thermal Enthalpies= -706.896125 Sum of electronic and thermal Free Energies= -706.950364 ωb97xd /6-311++G (d, p) /SMD//ωB97XD /6-31G(d) energy= -707.152270 dba 1 6 0-0.000575-0.921643 0.109025 2 8 0 0.003436-2.143880 0.167732 3 6 0 1.256205-0.132909 0.053810 4 6 0 2.446746-0.748840 0.070078 5 1 0 1.167025 0.948967-0.008457 6 1 0 2.421592-1.836431 0.133473 7 6 0-1.263339-0.140738 0.080412 8 6 0-2.449638-0.764662 0.068817 9 1 0-1.184342 0.943415 0.048159 10 1 0-2.420090-1.853982 0.070496 11 6 0-3.778842-0.147102 0.029180 12 6 0-4.889174-0.953615-0.251191 13 6 0-3.988977 1.220205 0.258064 14 6 0-6.167435-0.411360-0.322627 15 1 0-4.741625-2.016730-0.422490 16 6 0-5.265039 1.762019 0.191961 17 1 0-3.149571 1.863322 0.505016 18 6 0-6.358809 0.949087-0.102758 19 1 0-7.014164-1.052433-0.548659 20 1 0-5.410420 2.822392 0.375178 21 1 0-7.355679 1.376314-0.155254 22 6 0 3.775753-0.133310 0.007212 23 6 0 4.902778-0.964725 0.031642 24 6 0 3.972733 1.252407-0.081479 25 6 0 6.186255-0.433709-0.032036 26 1 0 4.765146-2.040613 0.101582 27 6 0 5.252806 1.784070-0.145017 28 1 0 3.118725 1.922607-0.101817 29 6 0 6.364853 0.942980-0.121287 30 1 0 7.046184-1.096417-0.013060 31 1 0 5.386845 2.859302-0.215614 6

32 1 0 7.365074 1.362406-0.173236 0.262074 (Hartree/Particle) Thermal correction to Energy= 0.277354 Thermal correction to Enthalpy= 0.278299 Thermal correction to Gibbs Free Energy= 0.216208 Sum of electronic and zero-point Energies= -730.924293 Sum of electronic and thermal Energies= -730.909013 Sum of electronic and thermal Enthalpies= -730.908069 Sum of electronic and thermal Free Energies= -730.970159 ωb97xd /6-311++G (d, p) /SMD//ωB97XD /6-31G(d) energy= -731.171558 CsF 1 55 0 0.000000 0.000000 0.360094 2 9 0 0.000000 0.000000-2.200575 0.000757 (Hartree/Particle) Thermal correction to Energy= 0.003499 Thermal correction to Enthalpy= 0.004443 Thermal correction to Gibbs Free Energy= -0.023356 Sum of electronic and zero-point Energies= -119.684357 Sum of electronic and thermal Energies= -119.681615 Sum of electronic and thermal Enthalpies= -119.680671 Sum of electronic and thermal Free Energies= -119.708470 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -119.864931 HF 1 9 0 0.000000 0.000000 0.092713 2 1 0 0.000000 0.000000-0.834421 0.009290 (Hartree/Particle) Thermal correction to Energy= 0.011651 Thermal correction to Enthalpy= 0.012595 Thermal correction to Gibbs Free Energy= -0.007126 Sum of electronic and zero-point Energies= -100.388119 Sum of electronic and thermal Energies= -100.385758 Sum of electronic and thermal Enthalpies= -100.384814 Sum of electronic and thermal Free Energies= -100.404535 ωb97xd /6-311++G (d, p) /SMD//ωB97XD /6-31G(d) energy= -100.469242 [PhCON-Ar] Cs + 1 6 0 6.040622 0.737891 0.370848 2 6 0 4.653208 0.837280 0.343727 3 6 0 3.869345-0.285764 0.077034 4 6 0 5.877528-1.612984-0.141638 5 6 0 6.655672-0.488324 0.128102 6 1 0 6.643565 1.616413 0.584450 7 1 0 4.152574 1.780925 0.533604 8 1 0 6.354014-2.570828-0.330913 9 1 0 7.739133-0.568919 0.150250 10 6 0 2.372730-0.148296 0.072775 11 8 0 1.869251 0.991629 0.240032 12 7 0 1.698391-1.274084-0.167895 13 6 0 0.358122-1.241416-0.005059 14 6 0-0.523903-1.546359-1.062882 15 6 0-0.273898-0.914162 1.219123 16 6 0-1.898221-1.423032-0.946660 17 6 0-1.644211-0.791745 1.332204 18 6 0-2.505367-1.040785 0.255086 7

19 6 0 4.490483-1.512523-0.165805 20 1 0 3.868745-2.377068-0.373058 21 55 0-0.693428 2.131741-0.476702 22 9 0 0.474083-0.611256 2.281264 23 9 0-2.141449-0.343821 2.492498 24 9 0-2.632258-1.603607-2.049455 25 9 0-0.019600-1.835181-2.265868 26 6 0-3.954680-0.675499 0.341139 27 9 0-4.484606-0.931568 1.539347 28 9 0-4.107464 0.668122 0.131863 29 9 0-4.707241-1.287841-0.573946 0.170537 (Hartree/Particle) Thermal correction to Energy= 0.191647 Thermal correction to Enthalpy= 0.192592 Thermal correction to Gibbs Free Energy= 0.116090 Sum of electronic and zero-point Energies= -1384.712916 Sum of electronic and thermal Energies= -1384.691805 Sum of electronic and thermal Enthalpies= -1384.690861 Sum of electronic and thermal Free Energies= -1384.767363 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -1385.223442 INT1 1 6 0 0.063210-2.517976 1.028749 2 8 0 0.049825-2.499210 2.253270 3 6 0 1.301527-2.387784 0.218034 4 6 0 2.454397-1.825168 0.802588 5 1 0 1.336081-2.927123-0.728453 6 1 0 2.407794-1.660516 1.878954 7 6 0-1.205474-2.573141 0.238109 8 6 0-2.387473-2.424985 0.848790 9 1 0-1.111743-2.651975-0.842458 10 1 0-2.356997-2.328857 1.933681 11 6 0-3.713678-2.336557 0.224725 12 6 0-4.832158-2.128945 1.042278 13 6 0-3.914674-2.418999-1.161606 14 6 0-6.107975-2.009288 0.500142 15 1 0-4.693202-2.056787 2.117732 16 6 0-5.186184-2.292458-1.706225 17 1 0-3.067584-2.577715-1.822449 18 6 0-6.290500-2.089057-0.877569 19 1 0-6.959499-1.851969 1.155742 20 1 0-5.319467-2.359374-2.781995 21 1 0-7.284145-1.996156-1.305933 22 6 0 3.821093-1.897444 0.240912 23 6 0 4.917623-1.682042 1.085049 24 6 0 4.076293-2.159186-1.113737 25 6 0 6.221242-1.728540 0.599984 26 1 0 4.740706-1.482631 2.139317 27 6 0 5.376702-2.211285-1.598721 28 1 0 3.244291-2.302035-1.797559 29 6 0 6.458009-1.994784-0.745081 30 1 0 7.053467-1.560145 1.277874 31 1 0 5.548718-2.414835-2.652030 32 1 0 7.473737-2.032776-1.127684 33 46 0 1.254551-0.329315-0.124443 34 6 0 2.029934 2.472087 1.168787 35 6 0 2.149611 3.992357 1.207915 36 6 0 2.038191 4.133068-1.114572 37 6 0 1.926040 2.619286-1.251332 38 1 0 1.156702 4.451841 1.332012 39 1 0 2.776037 4.294600 2.050774 40 1 0 3.021697 2.011469 1.138440 41 1 0 1.493119 2.075539 2.032502 42 1 0 1.036529 4.589305-1.081609 43 1 0 2.576341 4.547032-1.970662 8

44 1 0 1.321125 2.320472-2.110034 45 1 0 2.918241 2.170850-1.360702 46 7 0 1.348325 1.986036-0.046416 47 8 0 2.773921 4.480613 0.039232 48 8 0-0.010701 2.467118 0.085866 49 6 0-0.917554 1.656593-0.507742 50 8 0-0.603144 0.716395-1.210267 51 6 0-2.313664 2.027973-0.196500 52 6 0-2.652069 3.197290 0.491125 53 6 0-3.306619 1.127573-0.590716 54 6 0-3.986574 3.461059 0.774486 55 1 0-1.878713 3.892212 0.800034 56 6 0-4.637301 1.390056-0.293799 57 1 0-3.022932 0.219202-1.109486 58 6 0-4.976027 2.558009 0.386235 59 1 0-4.255993 4.369637 1.303891 60 1 0-5.400333 0.675651-0.585500 61 1 0-6.016500 2.765718 0.618208 0.498302 (Hartree/Particle) Thermal correction to Energy= 0.529125 Thermal correction to Enthalpy= 0.530069 Thermal correction to Gibbs Free Energy= 0.429944 Sum of electronic and zero-point Energies= -1564.614287 Sum of electronic and thermal Energies= -1564.583464 Sum of electronic and thermal Enthalpies= -1564.582520 Sum of electronic and thermal Free Energies= -1564.682646 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -1565.105650 TS1 1 6 0 0.129528-2.697223 0.905398 2 8 0 0.257671-2.904341 2.104209 3 6 0 1.270815-2.343695 0.016164 4 6 0 2.503529-1.946320 0.564440 5 1 0 1.174924-2.622102-1.032275 6 1 0 2.578189-2.005080 1.650093 7 6 0-1.204323-2.664629 0.243647 8 6 0-2.329831-2.663275 0.967781 9 1 0-1.218652-2.507202-0.831531 10 1 0-2.219532-2.750405 2.048033 11 6 0-3.692380-2.473878 0.453353 12 6 0-4.701639-2.078318 1.340174 13 6 0-4.020047-2.629540-0.901538 14 6 0-5.992582-1.824158 0.889271 15 1 0-4.463336-1.954705 2.393295 16 6 0-5.309709-2.379321-1.353428 17 1 0-3.261914-2.958262-1.605841 18 6 0-6.301122-1.973549-0.460033 19 1 0-6.757631-1.510254 1.592951 20 1 0-5.544698-2.508857-2.405734 21 1 0-7.309902-1.783512-0.814906 22 6 0 3.794616-1.875401-0.153411 23 6 0 4.959336-1.616438 0.581009 24 6 0 3.912322-2.038388-1.541126 25 6 0 6.197395-1.517793-0.044257 26 1 0 4.885411-1.490924 1.658592 27 6 0 5.149081-1.943410-2.166764 28 1 0 3.026970-2.234308-2.138875 29 6 0 6.298611-1.680139-1.423261 30 1 0 7.085989-1.317107 0.547473 31 1 0 5.217643-2.076524-3.242712 32 1 0 7.263737-1.604836-1.915041 33 46 0 1.280752-0.235065 0.136153 34 6 0 1.885473 2.319535 1.709366 35 6 0 1.790618 3.842873 1.713753 36 6 0 2.266413 3.966749-0.555174 9

37 6 0 2.396801 2.451547-0.674308 38 1 0 0.751904 4.153738 1.549720 39 1 0 2.129114 4.226334 2.679738 40 1 0 2.891523 2.017013 2.033647 41 1 0 1.164177 1.855732 2.384618 42 1 0 1.237398 4.271314-0.784990 43 1 0 2.946989 4.448363-1.261893 44 1 0 2.026537 2.076573-1.630686 45 1 0 3.455882 2.166896-0.591843 46 7 0 1.745814 1.697116 0.394830 47 8 0 2.640138 4.400696 0.733919 48 8 0-0.111106 2.419622 0.108344 49 6 0-0.951683 1.559265-0.322398 50 8 0-0.716707 0.359286-0.578101 51 6 0-2.357271 2.052384-0.505596 52 6 0-2.668167 3.411582-0.433097 53 6 0-3.368175 1.113647-0.722900 54 6 0-3.985706 3.828688-0.587881 55 1 0-1.876881 4.132162-0.255597 56 6 0-4.685691 1.533252-0.865202 57 1 0-3.114273 0.060717-0.768045 58 6 0-4.994311 2.890394-0.800910 59 1 0-4.226819 4.886275-0.536078 60 1 0-5.465990 0.794183-1.019650 61 1 0-6.023453 3.219189-0.914706 0.496572 (Hartree/Particle) Thermal correction to Energy= 0.526885 Thermal correction to Enthalpy= 0.527830 Thermal correction to Gibbs Free Energy= 0.430200 Sum of electronic and zero-point Energies= -1564.584236 Sum of electronic and thermal Energies= -1564.553923 Sum of electronic and thermal Enthalpies= -1564.552979 Sum of electronic and thermal Free Energies= -1564.650608 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -1565.077194 INT2 1 6 0-0.265448-2.390727 0.690396 2 8 0-0.131173-2.902002 1.791928 3 6 0 0.920398-2.023338-0.149257 4 6 0 2.191673-2.250436 0.309373 5 1 0 0.727057-1.703266-1.168894 6 1 0 2.281742-2.727193 1.285508 7 6 0-1.577628-2.060043 0.100622 8 6 0-2.702692-2.170003 0.822076 9 1 0-1.580445-1.650182-0.905655 10 1 0-2.595770-2.541043 1.840970 11 6 0-4.053483-1.794400 0.398822 12 6 0-5.060528-1.700943 1.367805 13 6 0-4.375043-1.498207-0.933047 14 6 0-6.348870-1.307134 1.023469 15 1 0-4.823753-1.930623 2.403663 16 6 0-5.661870-1.112520-1.278503 17 1 0-3.613863-1.561283-1.703694 18 6 0-6.652357-1.012227-0.302539 19 1 0-7.115575-1.235021 1.789021 20 1 0-5.891245-0.879560-2.313695 21 1 0-7.658468-0.708286-0.576483 22 6 0 3.439552-2.006050-0.435604 23 6 0 4.656672-2.402485 0.137934 24 6 0 3.459472-1.337187-1.674374 25 6 0 5.860630-2.149763-0.506235 26 1 0 4.649353-2.911516 1.097999 27 6 0 4.667496-1.079463-2.309660 28 1 0 2.533338-0.995037-2.127715 29 6 0 5.869083-1.485135-1.730766 10

30 1 0 6.793553-2.466617-0.050632 31 1 0 4.670309-0.558649-3.262181 32 1 0 6.810326-1.282568-2.232538 33 46 0 1.786681-0.042877 0.667664 34 6 0 2.050843 2.498377 2.123777 35 6 0 1.098358 3.530384 1.509597 36 6 0 2.166661 3.383629-0.549075 37 6 0 3.167595 2.367017 0.001757 38 1 0 0.204363 3.017709 1.133028 39 1 0 0.799732 4.261193 2.266001 40 1 0 2.880813 3.026108 2.618111 41 1 0 1.538330 1.899473 2.881686 42 1 0 1.318503 2.855172-1.008009 43 1 0 2.643550 4.006374-1.311017 44 1 0 3.500934 1.672748-0.776465 45 1 0 4.056059 2.906954 0.364128 46 7 0 2.654011 1.607357 1.138887 47 8 0 1.732336 4.251777 0.474476 48 8 0 0.097160 0.655381-1.667692 49 6 0-0.569329 0.872314-0.650828 50 8 0-0.143985 0.732628 0.562450 51 6 0-2.001680 1.321504-0.751349 52 6 0-2.538374 1.595190-2.010405 53 6 0-2.803914 1.441139 0.385390 54 6 0-3.864145 1.997145-2.131011 55 1 0-1.898637 1.489446-2.880468 56 6 0-4.131035 1.836970 0.262826 57 1 0-2.378310 1.206318 1.354617 58 6 0-4.661101 2.117688-0.994019 59 1 0-4.278978 2.212290-3.111610 60 1 0-4.758124 1.909340 1.146199 61 1 0-5.700519 2.418532-1.088975 0.497034 (Hartree/Particle) Thermal correction to Energy= 0.528215 Thermal correction to Enthalpy= 0.529159 Thermal correction to Gibbs Free Energy= 0.430216 Sum of electronic and zero-point Energies= -1564.620715 Sum of electronic and thermal Energies= -1564.589535 Sum of electronic and thermal Enthalpies= -1564.588591 Sum of electronic and thermal Free Energies= -1564.687534 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -1565.115615 INT3 1 46 0 2.492089-0.098288 0.006756 2 6 0 4.451699-1.619238-1.402166 3 6 0 5.897798-2.122788-1.451225 4 6 0 5.887290-2.465254 0.848331 5 6 0 4.439300-1.974866 0.935069 6 1 0 6.584749-1.263017-1.379921 7 1 0 6.088182-2.649388-2.390825 8 1 0 3.768623-2.469604-1.564677 9 1 0 4.298555-0.889280-2.204745 10 1 0 6.572104-1.621059 1.034503 11 1 0 6.073989-3.242879 1.594266 12 1 0 4.261875-1.522373 1.915751 13 1 0 3.764970-2.839641 0.829405 14 7 0 4.211032-0.987904-0.112667 15 8 0 6.156227-3.039405-0.412079 16 8 0 0.995792-1.972634 1.754527 17 6 0 0.754804-2.253559 0.581277 18 8 0 1.373169-1.789058-0.455682 19 6 0-0.429405-3.129177 0.242586 20 6 0-1.281251-3.534217 1.270246 21 6 0-0.750907-3.435354-1.081225 22 6 0-2.455387-4.220670 0.977480 11

23 1 0-1.014213-3.279015 2.290770 24 6 0-1.922603-4.125791-1.374595 25 1 0-0.084772-3.101736-1.869722 26 6 0-2.780516-4.511792-0.346229 27 1 0-3.124663-4.518765 1.779187 28 1 0-2.174106-4.350334-2.407095 29 1 0-3.704163-5.035385-0.576001 30 6 0 3.606187 4.813816-0.560129 31 6 0 2.332999 4.255017-0.530567 32 6 0 2.093981 3.086541 0.191739 33 6 0 4.413599 3.066815 0.892271 34 6 0 4.651063 4.215095 0.142575 35 1 0 3.787577 5.716791-1.136014 36 1 0 1.510127 4.707165-1.074876 37 1 0 5.216505 2.602193 1.455827 38 1 0 5.645766 4.649654 0.111857 39 6 0 0.730055 2.462384 0.133045 40 8 0-0.285331 3.179569-0.003898 41 7 0 0.733655 1.127873 0.195555 42 6 0-0.501204 0.497561 0.144353 43 6 0-1.249949 0.254644 1.299132 44 6 0-1.034287 0.038082-1.060716 45 6 0-2.490461-0.360231 1.238396 46 6 0-2.274428-0.582522-1.124087 47 6 0-3.037384-0.786928 0.025760 48 6 0 3.137707 2.508899 0.925007 49 1 0 2.939008 1.657933 1.579708 50 55 0-3.167276 2.876963-0.230396 51 6 0-4.459845-1.268879-0.033488 52 9 0-0.378220 0.258040-2.195957 53 9 0-2.745408-0.909105-2.328525 54 9 0-3.196812-0.465590 2.367443 55 9 0-0.816653 0.702859 2.471816 56 9 0-4.731197-1.980321-1.124420 57 9 0-5.293602-0.183181-0.059106 58 9 0-4.810422-1.991156 1.028016 0.405026 (Hartree/Particle) Thermal correction to Energy= 0.442571 Thermal correction to Enthalpy= 0.443515 Thermal correction to Gibbs Free Energy= 0.327707 Sum of electronic and zero-point Energies= -2218.440854 Sum of electronic and thermal Energies= -2218.403310 Sum of electronic and thermal Enthalpies= -2218.402366 Sum of electronic and thermal Free Energies= -2218.518173 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.191238 TS2 1 46 0 2.369102-0.221758-0.246927 2 6 0 4.967738-1.300927-1.049540 3 6 0 6.401398-1.655821-0.653521 4 6 0 5.705048-2.289619 1.480113 5 6 0 4.251226-1.962408 1.145787 6 1 0 6.906551-0.750630-0.271718 7 1 0 6.961621-2.035611-1.513266 8 1 0 4.502891-2.172706-1.539016 9 1 0 4.973597-0.472756-1.768335 10 1 0 6.180413-1.409113 1.945081 11 1 0 5.765224-3.131966 2.175185 12 1 0 3.717164-1.626758 2.038885 13 1 0 3.745912-2.868470 0.777528 14 7 0 4.231200-0.910885 0.140549 15 8 0 6.426508-2.670471 0.324699 16 8 0 0.826244-2.045608 1.587291 17 6 0 0.615156-2.340606 0.410646 18 8 0 1.306194-1.948957-0.609142 12

19 6 0-0.615544-3.143187 0.050542 20 6 0-1.499165-3.515583 1.063680 21 6 0-0.945364-3.403972-1.281185 22 6 0-2.710077-4.125388 0.750166 23 1 0-1.226651-3.294239 2.090684 24 6 0-2.154872-4.015537-1.596055 25 1 0-0.253622-3.094592-2.057439 26 6 0-3.042826-4.369030-0.581360 27 1 0-3.401505-4.399604 1.541513 28 1 0-2.411407-4.204428-2.634491 29 1 0-3.993631-4.833237-0.827398 30 6 0 3.880282 4.499588-0.167880 31 6 0 2.585080 4.017802-0.003147 32 6 0 2.328003 2.651889 0.073897 33 6 0 4.687204 2.232204-0.202738 34 6 0 4.933936 3.602062-0.279496 35 1 0 4.060821 5.569113-0.223289 36 1 0 1.739404 4.695771 0.054052 37 1 0 5.518725 1.533203-0.263109 38 1 0 5.948792 3.961413-0.424210 39 6 0 0.878067 2.239252 0.103734 40 8 0-0.024565 3.065585 0.340350 41 7 0 0.670936 0.956186-0.232217 42 6 0-0.599851 0.423056-0.126246 43 6 0-1.230448 0.252026 1.113199 44 6 0-1.284909-0.032908-1.251954 45 6 0-2.508681-0.269275 1.201790 46 6 0-2.567263-0.561833-1.163307 47 6 0-3.211796-0.682597 0.066024 48 6 0 3.398241 1.728901-0.001659 49 1 0 3.818422 0.525321 0.377775 50 55 0-2.941398 3.085243-0.019878 51 6 0-4.662206-1.059635 0.180259 52 9 0-0.737433 0.097703-2.456253 53 9 0-3.181842-0.885524-2.300157 54 9 0-3.094711-0.301526 2.402176 55 9 0-0.636646 0.680788 2.218975 56 9 0-5.113290-1.747465-0.865329 57 9 0-5.409487 0.082617 0.251360 58 9 0-4.930454-1.761080 1.280237 0.401258 (Hartree/Particle) Thermal correction to Energy= 0.437820 Thermal correction to Enthalpy= 0.438764 Thermal correction to Gibbs Free Energy= 0.328380 Sum of electronic and zero-point Energies= -2218.406959 Sum of electronic and thermal Energies= -2218.370397 Sum of electronic and thermal Enthalpies= -2218.369453 Sum of electronic and thermal Free Energies= -2218.479837 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.158239 INT4 1 46 0 2.414568 0.082786-0.109559 2 6 0 5.038658-0.964055-1.194769 3 6 0 6.390002-1.638773-0.981201 4 6 0 5.585244-2.811000 0.866867 5 6 0 4.201529-2.196065 0.715324 6 1 0 7.031032-0.989665-0.355826 7 1 0 6.895447-1.796367-1.937592 8 1 0 4.420391-1.555756-1.875790 9 1 0 5.158087 0.037382-1.618120 10 1 0 6.193314-2.212894 1.570062 11 1 0 5.510316-3.827290 1.261004 12 1 0 3.680566-2.090836 1.669344 13 1 0 3.572857-2.808948 0.066752 14 7 0 4.297796-0.859139 0.080205 13

15 8 0 6.249800-2.904239-0.378081 16 8 0 1.073952-2.011993 1.781678 17 6 0 0.797559-2.247239 0.601066 18 8 0 1.409784-1.786786-0.431791 19 6 0-0.418468-3.095081 0.282904 20 6 0-1.269414-3.483271 1.317753 21 6 0-0.752142-3.411812-1.035436 22 6 0-2.453132-4.159443 1.038019 23 1 0-0.991476-3.223731 2.334470 24 6 0-1.930387-4.096625-1.317151 25 1 0-0.086635-3.088157-1.828956 26 6 0-2.787593-4.462894-0.280910 27 1 0-3.121907-4.442056 1.845915 28 1 0-2.188868-4.329629-2.346209 29 1 0-3.717199-4.980458-0.500441 30 6 0 3.723803 4.695280 0.362865 31 6 0 2.398260 4.276663 0.296501 32 6 0 2.109638 2.924320 0.150569 33 6 0 4.441006 2.391028 0.136773 34 6 0 4.740996 3.748065 0.279161 35 1 0 3.963045 5.748380 0.478939 36 1 0 1.576548 4.985197 0.357774 37 1 0 5.273776 1.691470 0.069687 38 1 0 5.779993 4.065860 0.326204 39 6 0 0.705565 2.441496 0.072174 40 8 0-0.293302 3.179924 0.172824 41 7 0 0.656510 1.110647-0.148722 42 6 0-0.564769 0.462335-0.086171 43 6 0-1.240161 0.286455 1.127991 44 6 0-1.164935-0.073665-1.225224 45 6 0-2.482743-0.321839 1.179155 46 6 0-2.411851-0.684797-1.175239 47 6 0-3.104707-0.812014 0.027771 48 6 0 3.119369 1.945250 0.073396 49 1 0 4.826919-0.254241 0.708722 50 55 0-3.162330 2.905526-0.244517 51 6 0-4.532943-1.276165 0.087017 52 9 0-0.575923 0.060275-2.408708 53 9 0-2.953795-1.082444-2.326673 54 9 0-3.120187-0.358058 2.353113 55 9 0-0.730677 0.791166 2.244222 56 9 0-4.888707-2.029237-0.950574 57 9 0-5.353153-0.180741 0.073850 58 9 0-4.816503-1.949082 1.200272 0.408589 (Hartree/Particle) Thermal correction to Energy= 0.445128 Thermal correction to Enthalpy= 0.446072 Thermal correction to Gibbs Free Energy= 0.336311 Sum of electronic and zero-point Energies= -2218.491395 Sum of electronic and thermal Energies= -2218.454857 Sum of electronic and thermal Enthalpies= -2218.453912 Sum of electronic and thermal Free Energies= -2218.563673 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.242717 INT5 1 46 0-1.786380-0.260665-0.170344 2 6 0-0.608163-2.740678-0.811517 3 6 0 0.241672-3.608792-1.745063 4 6 0-0.427332-2.350563-3.578171 5 6 0-1.294284-1.460335-2.683806 6 1 0 1.268722-3.205263-1.780260 7 1 0 0.280935-4.641103-1.384716 8 1 0-1.599828-3.210486-0.691195 9 1 0-0.125094-2.705006 0.174157 10 1 0 0.567700-1.888156-3.685478 14

11 1 0-0.878426-2.462390-4.568370 12 1 0-1.336795-0.453906-3.114439 13 1 0-2.318227-1.873031-2.655959 14 7 0-0.682744-1.396374-1.364923 15 8 0-0.303033-3.650922-3.043072 16 8 0-3.537327 0.439348 1.108683 17 6 0-4.165876-0.541196 0.626898 18 8 0-3.590665-1.339998-0.187084 19 6 0-5.591358-0.785447 0.988001 20 6 0-6.242511 0.077074 1.871112 21 6 0-6.276916-1.868876 0.436299 22 6 0-7.575458-0.143610 2.200122 23 1 0-5.691369 0.913328 2.288390 24 6 0-7.609763-2.087548 0.766461 25 1 0-5.752638-2.526970-0.248332 26 6 0-8.259456-1.225078 1.647525 27 1 0-8.083248 0.527636 2.886598 28 1 0-8.142896-2.930269 0.336341 29 1 0-9.301661-1.395434 1.902788 30 6 0-1.674686 4.998696-1.949858 31 6 0-0.664890 4.112109-1.595803 32 6 0-0.900177 3.117352-0.642937 33 6 0-3.153861 3.938954-0.368789 34 6 0-2.924023 4.911868-1.337146 35 1 0-1.488943 5.758357-2.703890 36 1 0 0.315660 4.173113-2.056625 37 1 0-4.120586 3.866986 0.120085 38 1 0-3.713698 5.605094-1.612878 39 6 0 0.228232 2.194399-0.308688 40 8 0 1.400608 2.627829-0.364177 41 7 0-0.067427 0.932287 0.054827 42 6 0 1.032161 0.104544 0.230555 43 6 0 1.357855-0.409170 1.484583 44 6 0 1.834541-0.295905-0.847983 45 6 0 2.460633-1.235152 1.679891 46 6 0 2.928340-1.117199-0.655388 47 6 0 3.275463-1.604879 0.610875 48 6 0-2.146817 3.043317-0.020102 49 1 0-2.342023 2.297556 0.741136 50 55 0 4.053019 2.037047 0.621146 51 6 0 4.587549-2.314940 0.786771 52 9 0 0.639593-0.058091 2.549565 53 9 0 2.748013-1.599530 2.931079 54 9 0 1.636499 0.212225-2.057220 55 9 0 3.706416-1.395118-1.708374 56 9 0 4.816939-3.212048-0.171652 57 9 0 4.697861-2.933404 1.961254 58 9 0 5.602356-1.404274 0.726266 0.405626 (Hartree/Particle) Thermal correction to Energy= 0.442960 Thermal correction to Enthalpy= 0.443904 Thermal correction to Gibbs Free Energy= 0.328468 Sum of electronic and zero-point Energies= -2218.448590 Sum of electronic and thermal Energies= -2218.411256 Sum of electronic and thermal Enthalpies= -2218.410312 Sum of electronic and thermal Free Energies= -2218.525748 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.193493 TS3 1 46 0-1.699178 0.252573-0.493432 2 6 0-1.167086-2.450209 0.323005 3 6 0-0.457928-3.785043 0.086566 4 6 0-0.698326-3.531852-2.215142 5 6 0-1.420847-2.198726-2.013708 6 1 0 0.632110-3.607509 0.049928 15

7 1 0-0.672220-4.495820 0.890797 8 1 0-2.244473-2.645734 0.480528 9 1 0-0.770593-1.996669 1.241607 10 1 0 0.378368-3.335526-2.360411 11 1 0-1.083582-4.061936-3.091633 12 1 0-1.220664-1.551188-2.875174 13 1 0-2.509137-2.388259-1.970964 14 7 0-0.911840-1.572320-0.806387 15 8 0-0.887379-4.392859-1.111475 16 8 0-3.968995 1.008467 1.096076 17 6 0-4.359938 0.024694 0.382428 18 8 0-3.671451-0.485981-0.540891 19 6 0-5.707563-0.548058 0.657565 20 6 0-6.557945 0.059116 1.583671 21 6 0-6.113663-1.702760-0.014372 22 6 0-7.813072-0.485974 1.831222 23 1 0-6.223538 0.953230 2.098727 24 6 0-7.367408-2.246623 0.238111 25 1 0-5.436174-2.161501-0.726409 26 6 0-8.217753-1.637897 1.159368 27 1 0-8.476311-0.013397 2.549572 28 1 0-7.681961-3.146417-0.281890 29 1 0-9.197614-2.064000 1.355234 30 6 0-1.832467 5.193643-0.793407 31 6 0-0.754634 4.428049-0.361597 32 6 0-0.913994 3.067596-0.108432 33 6 0-3.222967 3.225422-0.713212 34 6 0-3.066830 4.583104-0.988373 35 1 0-1.705647 6.254643-0.989801 36 1 0 0.230722 4.866966-0.236328 37 1 0-4.206711 2.777607-0.831268 38 1 0-3.913118 5.164777-1.344215 39 6 0 0.325263 2.271125 0.149325 40 8 0 1.418067 2.797070 0.437216 41 7 0 0.159777 0.953472-0.081441 42 6 0 1.210839 0.085746 0.116988 43 6 0 1.759040-0.152543 1.380834 44 6 0 1.749207-0.635948-0.953028 45 6 0 2.858853-0.979508 1.548675 46 6 0 2.836685-1.479277-0.783243 47 6 0 3.425715-1.664651 0.471191 48 6 0-2.168288 2.429484-0.244582 49 1 0-2.941741 1.509491 0.554355 50 55 0 4.186268 2.012225-0.032034 51 6 0 4.742874-2.369874 0.635356 52 9 0 1.280478 0.491768 2.442277 53 9 0 3.415448-1.047050 2.762893 54 9 0 1.332796-0.398720-2.191176 55 9 0 3.351236-2.054456-1.872209 56 9 0 4.973719-3.276716-0.311531 57 9 0 4.860422-2.974914 1.817052 58 9 0 5.752081-1.453841 0.559719 0.400466 (Hartree/Particle) Thermal correction to Energy= 0.437045 Thermal correction to Enthalpy= 0.437989 Thermal correction to Gibbs Free Energy= 0.325256 Sum of electronic and zero-point Energies= -2218.415067 Sum of electronic and thermal Energies= -2218.378487 Sum of electronic and thermal Enthalpies= -2218.377543 Sum of electronic and thermal Free Energies= -2218.490277 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.161171 INT6 1 46 0-1.650389 0.453446-0.398977 2 6 0-1.149307-2.233780 0.723552 16

3 6 0-0.442787-3.588016 0.628776 4 6 0-0.803913-3.627849-1.675372 5 6 0-1.531789-2.285397-1.597143 6 1 0 0.642937-3.412883 0.517692 7 1 0-0.611207-4.194660 1.525023 8 1 0-2.215777-2.423202 0.975156 9 1 0-0.712500-1.666228 1.558351 10 1 0 0.261246-3.441422-1.899825 11 1 0-1.223011-4.273971-2.454147 12 1 0-1.399273-1.751787-2.546539 13 1 0-2.616208-2.492194-1.477145 14 7 0-0.980681-1.502321-0.513219 15 8 0-0.920853-4.345706-0.462069 16 8 0-4.201167 0.858265 1.328534 17 6 0-4.474328 0.036333 0.334010 18 8 0-3.685568-0.190619-0.585453 19 6 0-5.804028-0.604903 0.391631 20 6 0-6.747118-0.228697 1.351691 21 6 0-6.101300-1.604267-0.538776 22 6 0-7.989420-0.851093 1.373849 23 1 0-6.503256 0.545704 2.070386 24 6 0-7.343369-2.224872-0.508320 25 1 0-5.350425-1.885453-1.269450 26 6 0-8.286803-1.847065 0.445596 27 1 0-8.726201-0.559819 2.115665 28 1 0-7.576259-3.003876-1.227210 29 1 0-9.257700-2.333172 0.467651 30 6 0-1.869527 5.324651-0.115016 31 6 0-0.709490 4.582442 0.087065 32 6 0-0.762090 3.194109 0.007344 33 6 0-3.097062 3.268940-0.491399 34 6 0-3.059534 4.663807-0.410940 35 1 0-1.846132 6.408965-0.049771 36 1 0 0.240608 5.064579 0.301967 37 1 0-4.042751 2.787864-0.736756 38 1 0-3.967127 5.237660-0.584155 39 6 0 0.475889 2.383315 0.156663 40 8 0 1.606384 2.864808 0.358352 41 7 0 0.236425 1.060782-0.021690 42 6 0 1.246577 0.141564 0.147851 43 6 0 1.884453-0.053127 1.377005 44 6 0 1.644096-0.684940-0.909384 45 6 0 2.945082-0.935619 1.510412 46 6 0 2.693484-1.580667-0.771918 47 6 0 3.377208-1.721488 0.439751 48 6 0-1.953498 2.493179-0.271309 49 1 0-3.326518 1.279268 1.140226 50 55 0 4.258247 1.863920-0.381274 51 6 0 4.658195-2.497643 0.555224 52 9 0 1.533433 0.681868 2.430505 53 9 0 3.599827-0.964968 2.677362 54 9 0 1.152535-0.489241-2.127494 55 9 0 3.072065-2.261233-1.856555 56 9 0 4.788811-3.440149-0.376027 57 9 0 4.802488-3.078589 1.746727 58 9 0 5.713680-1.645042 0.403290 0.405212 (Hartree/Particle) Thermal correction to Energy= 0.442334 Thermal correction to Enthalpy= 0.443278 Thermal correction to Gibbs Free Energy= 0.327481 Sum of electronic and zero-point Energies= -2218.426752 Sum of electronic and thermal Energies= -2218.389631 Sum of electronic and thermal Enthalpies= -2218.388686 Sum of electronic and thermal Free Energies= -2218.504484 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.177155 TS4 17

1 46 0-1.558062 0.507453-0.189741 2 6 0-1.579185-2.364844-1.344794 3 6 0-2.666572-3.326387-0.859494 4 6 0-1.783701-3.268159 1.304640 5 6 0-0.683316-2.310409 0.842780 6 1 0-3.566506-2.753053-0.570416 7 1 0-2.951333-4.046871-1.634645 8 1 0-0.765129-2.989172-1.773039 9 1 0-1.976270-1.751817-2.163851 10 1 0-2.638601-2.686715 1.694294 11 1 0-1.432642-3.945410 2.091834 12 1 0-0.402513-1.658850 1.683276 13 1 0 0.206969-2.939237 0.608340 14 7 0-1.077669-1.518205-0.292820 15 8 0-2.216489-4.093963 0.241185 16 8 0-3.932950-0.374064 1.531197 17 6 0-4.361700-0.210585 0.294296 18 8 0-3.625805 0.162302-0.620840 19 6 0-5.792920-0.500990 0.078611 20 6 0-6.597050-0.973941 1.119086 21 6 0-6.331241-0.299141-1.195122 22 6 0-7.940062-1.239545 0.881672 23 1 0-6.166564-1.132919 2.101354 24 6 0-7.674428-0.565663-1.425233 25 1 0-5.686542 0.063969-1.988295 26 6 0-8.478137-1.034748-0.387307 27 1 0-8.568226-1.607984 1.686470 28 1 0-8.096296-0.409190-2.412929 29 1 0-9.528567-1.242368-0.568609 30 6 0-1.626028 5.305774 0.409184 31 6 0-0.472008 4.538421 0.526314 32 6 0-0.546873 3.162217 0.327707 33 6 0-2.894955 3.304612-0.119186 34 6 0-2.832726 4.684567 0.084948 35 1 0-1.589183 6.380100 0.567062 36 1 0 0.486595 4.989148 0.770332 37 1 0-3.847319 2.847803-0.380157 38 1 0-3.735754 5.283467-0.010790 39 6 0 0.657742 2.300282 0.410068 40 8 0 1.818604 2.720624 0.567335 41 7 0 0.344314 0.990509 0.225683 42 6 0 1.345304 0.041491 0.238557 43 6 0 2.085952-0.236330 1.390308 44 6 0 1.669016-0.685918-0.913292 45 6 0 3.157094-1.118030 1.373632 46 6 0 2.719830-1.588832-0.923166 47 6 0 3.500344-1.818007 0.216579 48 6 0-1.751345 2.512481 0.004088 49 1 0-2.961740-0.201653 1.524063 50 55 0 4.339246 1.765909-0.560559 51 6 0 4.784717-2.593495 0.132770 52 9 0 1.813016 0.405225 2.523373 53 9 0 3.891547-1.231632 2.484375 54 9 0 1.075607-0.407499-2.067875 55 9 0 3.043696-2.157151-2.087887 56 9 0 4.748627-3.564032-0.778006 57 9 0 5.140744-3.138516 1.295403 58 9 0 5.794766-1.748761-0.230762 0.404600 (Hartree/Particle) Thermal correction to Energy= 0.440990 Thermal correction to Enthalpy= 0.441934 Thermal correction to Gibbs Free Energy= 0.329865 Sum of electronic and zero-point Energies= -2218.421460 Sum of electronic and thermal Energies= -2218.385070 Sum of electronic and thermal Enthalpies= -2218.384126 Sum of electronic and thermal Free Energies= -2218.496195 18

ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.172428 INT7 1 46 0 1.716443 0.328808-0.110684 2 6 0 1.534884-2.588540 1.085387 3 6 0 1.760670-4.084781 0.896187 4 6 0 0.859396-4.024343-1.250850 5 6 0 0.589581-2.526815-1.140767 6 1 0 2.774827-4.250454 0.496812 7 1 0 1.664905-4.619372 1.845290 8 1 0 0.574687-2.411620 1.580879 9 1 0 2.324657-2.153193 1.704781 10 1 0 1.850447-4.189297-1.705897 11 1 0 0.104903-4.513335-1.874102 12 1 0 0.676994-2.036884-2.115563 13 1 0-0.430590-2.380198-0.770561 14 7 0 1.530990-1.890092-0.209750 15 8 0 0.797583-4.639129 0.019452 16 8 0 4.210170-1.781309-0.879885 17 6 0 4.538367-0.778777-0.222587 18 8 0 3.755897 0.122213 0.243122 19 6 0 5.998598-0.564960 0.096859 20 6 0 6.945762-1.452126-0.416199 21 6 0 6.414812 0.499175 0.898738 22 6 0 8.296918-1.272625-0.139176 23 1 0 6.600560-2.274630-1.033795 24 6 0 7.766002 0.677297 1.178868 25 1 0 5.668133 1.175632 1.300741 26 6 0 8.708950-0.207002 0.658802 27 1 0 9.030288-1.964698-0.543738 28 1 0 8.084691 1.506468 1.804487 29 1 0 9.764448-0.065350 0.874731 30 6 0 1.945920 5.096606-0.486929 31 6 0 0.740888 4.407310-0.540089 32 6 0 0.743773 3.020116-0.404732 33 6 0 3.132832 3.001236-0.155614 34 6 0 3.134841 4.389406-0.295395 35 1 0 1.965822 6.177152-0.598025 36 1 0-0.204276 4.922439-0.690342 37 1 0 4.062828 2.459766-0.016278 38 1 0 4.078632 4.928418-0.257765 39 6 0-0.503309 2.229354-0.433243 40 8 0-1.646490 2.720851-0.491411 41 7 0-0.256441 0.895701-0.319157 42 6 0-1.349113 0.060009-0.282441 43 6 0-2.201051-0.109776-1.383889 44 6 0-1.691099-0.640484 0.880371 45 6 0-3.349846-0.879584-1.303022 46 6 0-2.829107-1.431083 0.957204 47 6 0-3.694081-1.562364-0.131605 48 6 0 1.930096 2.298957-0.209184 49 1 0 2.484537-1.986191-0.605218 50 55 0-4.218450 2.082190 0.661869 51 6 0-5.041284-2.217834 0.005263 52 9 0-1.946150 0.528031-2.519594 53 9 0-4.166266-0.902058-2.358974 54 9 0-0.956654-0.490886 1.981364 55 9 0-3.122545-1.983007 2.134535 56 9 0-5.068562-3.155579 0.949224 57 9 0-5.463575-2.768100-1.131667 58 9 0-5.962649-1.275153 0.355406 0.408218 (Hartree/Particle) Thermal correction to Energy= 0.445230 Thermal correction to Enthalpy= 0.446174 Thermal correction to Gibbs Free Energy= 0.332007 19

Sum of electronic and zero-point Energies= -2218.487194 Sum of electronic and thermal Energies= -2218.450182 Sum of electronic and thermal Enthalpies= -2218.449238 Sum of electronic and thermal Free Energies= -2218.563405 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2219.239884 INT8 1 46 0 1.917487 0.489386-0.091307 2 8 0 0.458924-1.729929 1.845106 3 6 0-0.121160-2.283287 0.946409 4 8 0 0.344451-2.394095-0.318758 5 6 0-1.454838-2.937537 1.074831 6 6 0-2.104369-2.820976 2.305640 7 6 0-2.068729-3.616412 0.020100 8 6 0-3.371301-3.364395 2.475295 9 1 0-1.608306-2.285924 3.109053 10 6 0-3.336085-4.162072 0.195158 11 1 0-1.561747-3.705248-0.934454 12 6 0-3.988695-4.031854 1.418965 13 1 0-3.880741-3.260270 3.427793 14 1 0-3.818817-4.679676-0.627496 15 1 0-4.982342-4.449597 1.548881 16 6 0 2.539446 5.169757 0.618675 17 6 0 1.291271 4.567773 0.703627 18 6 0 1.173853 3.198736 0.467551 19 6 0 3.532704 3.026362 0.046492 20 6 0 3.651720 4.395527 0.282777 21 1 0 2.651396 6.233974 0.805730 22 1 0 0.398944 5.136769 0.950770 23 1 0 4.406963 2.443969-0.221791 24 1 0 4.629076 4.865338 0.204093 25 6 0-0.138300 2.525217 0.473234 26 8 0-1.217852 3.127072 0.632945 27 7 0-0.038555 1.195930 0.191761 28 6 0-1.231631 0.510695 0.139560 29 6 0-2.101436 0.418800 1.238498 30 6 0-1.683911-0.077459-1.048492 31 6 0-3.369624-0.128518 1.121852 32 6 0-2.942703-0.646628-1.159581 33 6 0-3.828477-0.671403-0.080960 34 6 0 2.286069 2.409345 0.151339 35 55 0-3.767076 2.987285-0.702356 36 6 0-5.258315-1.090901-0.268553 37 9 0-0.938270 0.008136-2.152987 38 9 0-3.322917-1.092629-2.359987 39 9 0-4.167516-0.080115 2.191187 40 9 0-1.743040 0.916724 2.412479 41 9 0-5.401534-2.059617-1.172969 42 9 0-5.982765-0.024516-0.720655 43 9 0-5.841436-1.495125 0.858493 44 6 0 1.780581-1.890171-2.032374 45 6 0 1.814050-3.331894-2.534471 46 6 0 2.629650-4.086187-0.487389 47 6 0 2.666327-2.669537 0.064809 48 1 0 0.828544-3.805188-2.397266 49 1 0 2.049846-3.339891-3.602031 50 1 0 2.724361-1.381721-2.248872 51 1 0 0.962092-1.329088-2.484723 52 1 0 1.685869-4.591120-0.226932 53 1 0 3.454985-4.662291-0.062787 54 1 0 2.547692-2.617800 1.146278 55 1 0 3.613304-2.199473-0.197128 56 7 0 1.638935-1.798479-0.562304 57 8 0 2.812798-4.087998-1.890071 58 8 0 4.225109-0.319926 1.739094 59 6 0 4.642761-0.132413 0.600594 20

60 8 0 3.915874 0.114642-0.447267 61 6 0 6.124210-0.205655 0.313320 62 6 0 6.995928-0.536341 1.351885 63 6 0 6.636023 0.045225-0.961108 64 6 0 8.364399-0.618430 1.120144 65 1 0 6.573269-0.721641 2.334015 66 6 0 8.006041-0.035430-1.193582 67 1 0 5.946954 0.303862-1.758082 68 6 0 8.871825-0.368677-0.154076 69 1 0 9.038433-0.877185 1.932132 70 1 0 8.400368 0.160485-2.186985 71 1 0 9.941150-0.434265-0.336155 0.503869 (Hartree/Particle) Thermal correction to Energy= 0.547895 Thermal correction to Enthalpy= 0.548839 Thermal correction to Gibbs Free Energy= 0.420324 Sum of electronic and zero-point Energies= -2637.815480 Sum of electronic and thermal Energies= -2637.771453 Sum of electronic and thermal Enthalpies= -2637.770509 Sum of electronic and thermal Free Energies= -2637.899024 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2638.692642 Morpholine 1 6 0-1.199103 0.721646-0.220017 2 6 0-1.168673-0.747788 0.198881 3 6 0 1.167636-0.749380 0.198776 4 6 0 1.200143 0.720072-0.219910 5 1 0-1.215596-0.820862 1.301015 6 1 0-2.016451-1.300337-0.216800 7 1 0-1.269733 0.778082-1.313508 8 1 0-2.081745 1.220403 0.195270 9 1 0 1.214632-0.822698 1.300880 10 1 0 2.014609-1.302995-0.217131 11 1 0 2.083380 1.217608 0.195598 12 1 0 1.270978 0.776637-1.313360 13 7 0 0.000969 1.449944 0.188848 14 8 0-0.000989-1.387835-0.275439 15 1 0 0.001031 1.539936 1.203226 0.137592 (Hartree/Particle) Thermal correction to Energy= 0.142812 Thermal correction to Enthalpy= 0.143756 Thermal correction to Gibbs Free Energy= 0.109194 Sum of electronic and zero-point Energies= -287.569076 Sum of electronic and thermal Energies= -287.563856 Sum of electronic and thermal Enthalpies= -287.562912 Sum of electronic and thermal Free Energies= -287.597474 ωb97xd /6-311++G (d, p) /SMD//ωB97XD /6-31G(d) energy= -287.690355 TS5 1 46 0 1.841428-0.290360 0.048582 2 8 0 0.900013 1.832864-0.276504 3 6 0 0.264147 2.406609 0.639596 4 8 0 0.528566 2.425679 1.882649 5 6 0-0.992463 3.148604 0.234524 6 6 0-1.215215 3.442440-1.112317 7 6 0-1.956033 3.488986 1.184337 8 6 0-2.394942 4.065336-1.506140 9 1 0-0.460077 3.155244-1.837040 10 6 0-3.144654 4.095082 0.788087 11 1 0-1.764657 3.263748 2.228347 12 6 0-3.365374 4.383545-0.557341 21

13 1 0-2.566106 4.286652-2.555325 14 1 0-3.901458 4.340103 1.527375 15 1 0-4.294287 4.853755-0.866622 16 6 0 2.776050-4.844188 1.067108 17 6 0 1.477092-4.359653 0.965307 18 6 0 1.267393-3.020790 0.644540 19 6 0 3.648222-2.644057 0.515280 20 6 0 3.852911-3.985415 0.842334 21 1 0 2.953476-5.885710 1.318474 22 1 0 0.615263-4.999984 1.132602 23 1 0 4.487972-1.980040 0.338883 24 1 0 4.868233-4.365608 0.921380 25 6 0-0.094138-2.447694 0.511683 26 8 0-1.140731-3.118182 0.563785 27 7 0-0.043768-1.114095 0.277695 28 6 0-1.225932-0.426938 0.075992 29 6 0-1.534583 0.111278-1.176528 30 6 0-2.178767-0.251675 1.086161 31 6 0-2.753905 0.727285-1.426165 32 6 0-3.397259 0.356204 0.836837 33 6 0-3.720043 0.852237-0.428058 34 6 0 2.348688-2.159094 0.413132 35 55 0-3.663403-2.861724-0.882075 36 6 0-5.123870 1.309196-0.712604 37 9 0-1.959455-0.749217 2.303343 38 9 0-4.297479 0.391701 1.822684 39 9 0-3.001967 1.120596-2.674196 40 9 0-0.689819-0.044700-2.186238 41 9 0-5.654485 2.008187 0.289053 42 9 0-5.916231 0.209305-0.886433 43 9 0-5.229926 2.034686-1.822578 44 6 0 1.297265-0.030548 3.149863 45 6 0 1.270881 0.832221 4.422522 46 6 0 2.986098 2.163766 3.623211 47 6 0 3.049897 1.361566 2.313850 48 1 0 0.528996 1.630668 4.291065 49 1 0 0.989975 0.213120 5.278195 50 1 0 1.981602-0.873527 3.317060 51 1 0 0.307108-0.422100 2.911004 52 1 0 2.317994 3.020881 3.473208 53 1 0 3.986009 2.519633 3.882280 54 1 0 3.323989 1.996715 1.470156 55 1 0 3.806461 0.570945 2.414599 56 7 0 1.780135 0.726944 2.011764 57 8 0 2.542778 1.362828 4.692584 58 8 0 3.193217 0.033391-2.393603 59 6 0 4.027389 0.290131-1.528021 60 8 0 3.794370 0.252333-0.250363 61 6 0 5.437817 0.666485-1.895053 62 6 0 5.769566 0.805841-3.243191 63 6 0 6.414925 0.870492-0.919298 64 6 0 7.065918 1.147211-3.613172 65 1 0 4.994237 0.641462-3.984211 66 6 0 7.713265 1.207625-1.289391 67 1 0 6.145565 0.760002 0.125701 68 6 0 8.039959 1.347435-2.636631 69 1 0 7.317891 1.258221-4.664072 70 1 0 8.471551 1.362354-0.526790 71 1 0 9.053866 1.611430-2.924927 0.499600 (Hartree/Particle) Thermal correction to Energy= 0.543942 Thermal correction to Enthalpy= 0.544886 Thermal correction to Gibbs Free Energy= 0.416222 Sum of electronic and zero-point Energies= -2637.762621 Sum of electronic and thermal Energies= -2637.718279 Sum of electronic and thermal Enthalpies= -2637.717335 Sum of electronic and thermal Free Energies= -2637.845998 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2638.637362 22

INT9 1 46 0 1.890062-0.328550 0.203580 2 8 0 1.086244 1.644633 0.499088 3 6 0 0.280804 2.076451 1.404403 4 8 0 0.247210 1.770485 2.596187 5 6 0-0.757527 3.053203 0.876151 6 6 0-0.722457 3.502555-0.445515 7 6 0-1.802851 3.451491 1.708824 8 6 0-1.731388 4.328717-0.932493 9 1 0 0.096493 3.178380-1.079821 10 6 0-2.819142 4.267906 1.221100 11 1 0-1.804013 3.092316 2.733346 12 6 0-2.786868 4.704182-0.102834 13 1 0-1.701348 4.671733-1.962900 14 1 0-3.638792 4.561938 1.870624 15 1 0-3.581761 5.338039-0.485885 16 6 0 2.992416-4.656202-1.446126 17 6 0 1.687186-4.175966-1.433131 18 6 0 1.433536-2.907155-0.921217 19 6 0 3.781276-2.591106-0.437907 20 6 0 4.030072-3.866323-0.949992 21 1 0 3.205024-5.644158-1.843292 22 1 0 0.858154-4.766893-1.812041 23 1 0 4.588836-1.976046-0.054300 24 1 0 5.047978-4.246656-0.961975 25 6 0 0.067301-2.331048-0.842755 26 8 0-0.961361-2.899680-1.245051 27 7 0 0.088096-1.115351-0.256131 28 6 0-1.076293-0.366633-0.143061 29 6 0-1.510133 0.433139-1.199826 30 6 0-1.867594-0.399932 1.006630 31 6 0-2.715553 1.120165-1.147230 32 6 0-3.062160 0.302779 1.067870 33 6 0-3.518694 1.065990-0.009068 34 6 0 2.477276-2.121818-0.427529 35 55 0-3.827773-2.353420-1.369917 36 6 0-4.914887 1.628947 0.016341 37 9 0-1.551861-1.203235 2.013293 38 9 0-3.824156 0.151507 2.152119 39 9 0-3.113366 1.761457-2.244871 40 9 0-0.801590 0.480388-2.320047 41 9 0-5.259489 2.109682 1.207050 42 9 0-5.793505 0.620319-0.271701 43 9 0-5.118565 2.579511-0.890135 44 6 0 1.559014-2.316412 2.399608 45 6 0 1.133998-2.447541 3.875100 46 6 0 2.098081-0.405133 4.375213 47 6 0 2.550044-0.231047 2.916912 48 1 0 0.113784-2.051108 3.985453 49 1 0 1.148017-3.502329 4.165665 50 1 0 2.543754-2.792311 2.269568 51 1 0 0.826387-2.834901 1.777051 52 1 0 1.125323 0.089929 4.491992 53 1 0 2.830079 0.053378 5.044791 54 1 0 2.550773 0.834701 2.685852 55 1 0 3.558510-0.655022 2.788028 56 7 0 1.549151-0.899203 2.108646 57 8 0 2.023434-1.771557 4.723156 58 8 0 2.949461 0.659981-1.652835 59 6 0 3.889906 0.852739-0.854037 60 8 0 3.827639 0.387480 0.347835 61 6 0 5.109026 1.611974-1.244914 62 6 0 5.213150 2.127449-2.537678 63 6 0 6.140667 1.811876-0.325979 64 6 0 6.347009 2.840900-2.909734 23

65 1 0 4.398143 1.962722-3.234703 66 6 0 7.273487 2.525430-0.701086 67 1 0 6.040639 1.408116 0.675781 68 6 0 7.377017 3.039841-1.991956 69 1 0 6.428498 3.245359-3.914324 70 1 0 8.074805 2.683654 0.014612 71 1 0 8.262122 3.598499-2.283240 0.501757 (Hartree/Particle) Thermal correction to Energy= 0.546037 Thermal correction to Enthalpy= 0.546981 Thermal correction to Gibbs Free Energy= 0.418835 Sum of electronic and zero-point Energies= -2637.794895 Sum of electronic and thermal Energies= -2637.750615 Sum of electronic and thermal Enthalpies= -2637.749671 Sum of electronic and thermal Free Energies= -2637.877817 ωb97xd /6-311++G (d, p)- LANL2TZ(f)/SMD//ωB97XD /6-31G(d)-LANL2DZ energy= -2638.672662 INT8a 1 46 0 1.796155-1.096099-0.100604 2 8 0 0.465640 0.983487-2.085119 3 6 0 0.539922 1.443439-0.947591 4 8 0 1.211546 0.947020 0.038152 5 6 0-0.278859 2.663970-0.585638 6 6 0-1.127357 3.216613-1.544759 7 6 0-0.279313 3.177372 0.711982 8 6 0-1.982753 4.260601-1.207624 9 1 0-1.112826 2.791697-2.543623 10 6 0-1.128014 4.226456 1.049530 11 1 0 0.385474 2.734215 1.445261 12 6 0-1.988195 4.763112 0.092874 13 1 0-2.655136 4.674949-1.953506 14 1 0-1.127390 4.620408 2.062060 15 1 0-2.664020 5.570676 0.360844 16 6 0 1.853496-5.958453-0.246755 17 6 0 0.697019-5.187347-0.255760 18 6 0 0.789220-3.800875-0.198136 19 6 0 3.165157-3.923358-0.111895 20 6 0 3.085213-5.317379-0.168989 21 1 0 1.796882-7.042021-0.296304 22 1 0-0.288780-5.641460-0.307329 23 1 0 4.160354-3.494450-0.043882 24 1 0 4.001550-5.902674-0.153055 25 6 0-0.442992-2.976050-0.172357 26 8 0-1.598300-3.443709-0.158310 27 7 0-0.151216-1.662530-0.114648 28 6 0-1.196443-0.752368-0.081807 29 6 0-1.971529-0.477585-1.213788 30 6 0-1.506680-0.050560 1.083003 31 6 0-3.032022 0.410605-1.157517 32 6 0-2.565642 0.847448 1.138599 33 6 0-3.358822 1.090913 0.019069 34 6 0 2.021754-3.118021-0.133191 35 55 0-4.268840-2.501213 0.500553 36 6 0-4.616386 1.911005 0.085050 37 9 0-0.815707-0.277057 2.195819 38 9 0-2.834849 1.417132 2.313643 39 9 0-3.796321 0.549485-2.245954 40 9 0-1.754047-1.137984-2.341110 41 9 0-4.631767 2.772339 1.098936 42 9 0-5.681954 1.073301 0.265376 43 9 0-4.851077 2.591162-1.035559 44 8 0 3.518503 1.462023-1.821563 45 6 0 3.562711 1.759950-0.656449 46 8 0 3.982070 0.922880 0.340698 47 6 0 3.256295 3.111202-0.113350 24