Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008
Pyridine Catalyzed Stereoselective Addition of Acyclic 1,2-Diones to Acetylenic Ester: Synthetic and Theoretical Studies of An Unprecedented Rearrangement Abhilash N. Pillai, [a] Cherumuttathu H. Suresh*, [b] and Vijay Nair* [a,c] [a] Abhilash N. Pillai, Vijay Nair Organic Chemistry Section National Institute for Interdisciplinary Science and Technology (CSIR),)) Trivandrum-695019 Fax: (+)91 471 2491712 E-mail: vijaynair_2001@yahoo.com [b] Cherumuttathu H. Suresh, Computational Modeling and Simulation Section National Institute for Interdisciplinary Science and Technology (CSIR) Trivandrum-695019 Fax: (+)91 471 2491712 E-mail: sureshch@gmail.com [c] Vijay Nair Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore - 560064
Supporting Information Contents General aspects General procedure for the preparation of benzil analogs General procedure for the reaction of benzil analogs with DMAD S2 S2 S3 1 H NMR Spectrums S4 Full reference for Gaussian 03 software S7
S2 Rotation experiment on 18 at B3LYP 6-31G(d) level PCM/B3LYP 6-31G(d) level structures of TS1 B3LYP 6-31+G(d,p) level structures of TS1 and TS2 B3LYP 6-31G(d) level structures S8 S8 S9 S9 General aspects: All reactions were carried out in oven-dried glassware under argon atmosphere. Progress of reaction was monitored by Thin Layer Chromatography (on glass plates coated with silica gel containing calciumsulfate as the binder; visualization was effected by exposure to UV light or iodine), while purification was effected by silica gel column chromatography (using 100-200 mesh silica gel and mixtures of hexane- ethyl acetate as the eluent). NMR data were collected at room temperature in CDCl3 at an operating frequency of 300 (1H) and 75 (13C) MHz, respectively. Chemical shifts (δ) are reported relative to TMS (1H) or CDCl3 (13C). Melting points are uncorrected. Elemental analyses were done using a CHNS analyzer. High Resolution Mass Spectra were recorded under EI/HRMS (at 5000 resolution). Commercial grade solvents were distilled prior to use. Dimethyl acetylenedicarboxylate was used directly. General procedure for the preparation of benzil analogs: A solution of 0.50 g of thiamine hydrochloride in 2 ml water and 5 ml of 95% ethanol were taken in a reaction vial. To it 3M sodium hydroxide solution was added dropwise till a yellow color persists in the solution. Then aldehyde was added to it and the reaction mixture is heated at 60 C for 12 h. Adequate precautions should be taken to maintain the temperature below 65 C. After completion of the reaction, the mixture was poured into ice cold water and extracted with dichloromethane (3 x 10 ml). The combined organic extract was washed with water, brine and then dried over anhydrous sodium sulphate. After removal of the solvent on a rotary evaporator, 3 ml of concentrated nitric acid was
S3 added to it and refluxed for 5 h. After completion of the reaction, the mixture was poured into ice cold water and stirred well. The product which was precipitated in the solution was filtered, washed with sodium bicarbonate solution and water. Then it was dried and recrystallized from dichloromethanehexane solvent mixture. General procedure for the reaction of benzil analogs with DMAD: Benzil (1 equiv) and dimethyl acetylenedicarboxylate (1.2 equiv.) were taken in anhydrous dimethoxy ethane (5 ml), the solution was stirred under argon atmosphere and cooled to 10 C. Pyridine (20 mol%) was added and the mixture was gradually allowed to attain room temperature. The reaction was monitored by TLC and the solvent was distilled off in vacuo by using a rotary evaporator. The residue when subjected to column chromatography on a silica (100-200 mesh) column first gave the unreacted benzil on using 5% ethyl acetate-hexane mixture as eluent. Subsequently, elution with 20% ethyl acetate-hexane mixture afforded the product which was recrystallized from dichloromethane-hexane solvent mixtures.
S4 Dimethyl (2Z)-2,3-dibenzoylbut-2-enedioate 7 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz
S5 Dimethyl (2Z)-2,3-diacetylbut-2-enedioate 9 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz
S6 Di-tert-butyl (2Z)-2,3-dibenzoylbut-2-enedioate 11 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz
S7 Full reference for Gaussian 03 software (ref. 13) Gaussian 03, Revision C.02, Frisch, M. J. et al. ; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Yengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; 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.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.: Wallingford CT, 2004.
S8 Rotation Experiment done on Structure 18 at B3LYP/6-31G(d) level N MeOOC 34 o C COMe COMe COOMe Fully optimized geometry of 18 Rel.Energy = 0.0 kcal/mol N MeOOC 90 o COMe C COMe COOMe Rel. Energy = 11.2 kcal/mol COOMe N COMe C MeOCCOOMe Rel. Energy = 2.2 kcal/mol 180 o N C COOMe COMe 164 o N MeOC C COMe COOMe MeOC COOMe COOMe 90 o Fully optimized geometry Rel. Energy = 0.7 kcal/mol Rel. Energy = 11.8 kcal/mol B3LYP 6-31G(d) level optimized structure of 15 in THF using the PCM method.
S9 B3LYP 6-31+G(d,p) level structures of TS1 and TS2 TS1 (Activation barrier is 0.7 kcal/mol lower than the values reported in the text). TS2 (Activation barrier is 1.0 Kcal/mol higher than the values reported in the text). B3LYP 6-31G(d) level optimized structures. The Cartesian coordinates in Angstrom unit are written against each atom (atomic number is given in the fist column followed by X, Y, Z coordinates). At the end, the thermodynamic parameters are given in atomic unit. Compound 15 6-1.787224000-3.166905000 0.384292000 6-3.027087000-3.344969000-0.229203000 6-3.673201000-2.231288000-0.764292000 6-3.078390000-0.982534000-0.674422000 7-1.877380000-0.825356000-0.066463000 6-1.237305000-1.899048000 0.456506000
S1 0 6-1.172404000 0.495688000-0.011013000 6-2.102454000 1.634887000 0.205451000 6 0.159575000 0.459457000-0.068316000 6 1.050504000 1.576655000 0.079860000 8-3.310526000 1.553414000 0.385107000 8-1.445991000 2.806747000 0.199593000 8 1.555181000 1.912819000 1.147818000 8 1.413381000 2.121990000-1.112971000 1-1.232677000-3.993554000 0.813572000 1-3.479082000-4.330053000-0.292408000 1-4.632348000-2.317090000-1.262747000 1-3.534926000-0.087431000-1.066034000 1-0.270917000-1.693077000 0.895138000 6 3.023494000-1.275667000-0.580658000 8 3.905853000-0.441091000-0.653767000 6 2.519154000-1.730060000 0.812235000 8 1.785487000-2.705131000 0.895415000 6 2.512324000 3.040916000-1.047058000 1 2.673593000 3.374722000-2.073715000 1 2.276529000 3.893165000-0.403426000 1 3.407343000 2.540964000-0.666297000 6-2.247250000 3.967183000 0.463310000 1-1.553837000 4.807506000 0.432331000 1-3.024717000 4.079684000-0.297430000 1-2.718751000 3.894075000 1.446850000 6 3.005745000-0.936929000 1.991649000 1 2.730037000-1.445728000 2.917890000 1 4.089196000-0.792468000 1.934265000 1 2.554083000 0.065128000 1.959952000 6 2.386471000-1.933282000-1.779871000 1 2.336216000-3.018472000-1.650108000 1 1.358588000-1.562077000-1.861921000 1 2.944548000-1.672406000-2.681047000 Zero-point correction= 0.303012 (Hartree/Particle) Thermal correction to Energy= 0.327428 Thermal correction to Enthalpy= 0.328372 Thermal correction to Gibbs Free Energy= 0.245259 Sum of electronic and zero-point Energies= -1087.534206 Sum of electronic and thermal Energies= -1087.509790 Sum of electronic and thermal Enthalpies= -1087.508846 Sum of electronic and thermal Free Energies= -1087.591959 TS1 6 3.584310000-0.754536000-1.026516000 6 4.381213000-0.404365000 0.049511000 6 3.833215000 0.368330000 1.085448000 6 2.521428000 0.775584000 0.999093000 7 1.756770000 0.444120000-0.076188000 6 2.252550000-0.345083000-1.054339000 6 0.343721000 0.865536000-0.141369000 6 0.210486000 2.346196000 0.002579000 6-0.592811000-0.062502000-0.351717000 6-2.016486000 0.214024000-0.517664000 8 1.141769000 3.103231000 0.222463000 8-1.058971000 2.752378000-0.139800000 8-2.569803000 0.289250000-1.601041000
S1 1 8-2.666926000 0.230509000 0.670007000 1 3.956816000-1.366074000-1.839725000 1 5.417990000-0.723232000 0.094438000 1 4.420966000 0.656363000 1.949337000 1 2.039846000 1.380236000 1.753086000 1 1.593987000-0.519599000-1.891201000 6-1.083779000-2.449251000 0.738099000 8-2.225617000-2.799458000 0.498115000 6-0.091206000-2.140267000-0.403046000 8 1.133178000-2.268929000-0.136361000 6-1.275459000 4.168462000-0.029376000 1-2.343671000 4.308991000-0.192331000 1-0.985350000 4.523520000 0.963071000 1-0.695738000 4.704036000-0.785336000 6-4.100370000 0.204448000 0.578536000 1-4.457065000 0.212490000 1.609286000 1-4.471254000 1.078858000 0.037168000 1-4.428770000-0.704986000 0.069454000 6-0.614621000-2.470384000-1.799337000 1 0.090878000-2.112247000-2.555388000 1-0.668124000-3.563469000-1.886201000 1-1.604425000-2.060458000-1.998573000 6-0.527914000-2.371463000 2.144452000 1 0.304584000-3.074325000 2.251499000 1-0.125422000-1.371649000 2.338899000 1-1.317335000-2.601510000 2.862637000 Zero-point correction= 0.303754 (Hartree/Particle) Thermal correction to Energy= 0.326761 Thermal correction to Enthalpy= 0.327706 Thermal correction to Gibbs Free Energy= 0.250201 Sum of electronic and zero-point Energies= -1087.525245 Sum of electronic and thermal Energies= -1087.502237 Sum of electronic and thermal Enthalpies= -1087.501293 Sum of electronic and thermal Free Energies= -1087.578797 Compound 16 6-3.584099000 0.286957000-0.879811000 6-4.281262000-0.718292000-0.319561000 6-3.606647000-1.812008000 0.342094000 6-2.257179000-1.839596000 0.379480000 7-1.491541000-0.858020000-0.236414000 6-2.094402000 0.340080000-0.835612000 6-0.113602000-0.770997000-0.156218000 6 0.622378000-2.066564000 0.091293000 6 0.500969000 0.432999000-0.360394000 6 1.957086000 0.569863000-0.532720000 8 0.357266000-3.114097000-0.457757000 8 1.555031000-1.923414000 1.046295000 8 2.599604000 1.547840000-0.183656000
S1 2 8 2.518672000-0.479128000-1.180882000 6 0.078723000 2.280499000 1.253879000 8-0.108268000 1.554178000 2.203014000 6-0.273064000 1.741053000-0.194514000 8-1.684794000 1.490006000-0.091986000 1-4.066502000 1.125009000-1.371926000 1-5.367150000-0.717212000-0.362722000 1-4.169170000-2.608967000 0.813298000 1-1.701253000-2.626612000 0.869817000 1-1.658326000 0.428386000-1.844279000 6 3.947113000-0.422027000-1.314441000 1 4.223379000-1.319557000-1.868772000 1 4.244890000 0.475473000-1.862298000 1 4.425693000-0.412235000-0.331097000 6 2.328233000-3.102785000 1.327580000 1 3.011538000-2.816673000 2.126876000 1 1.676624000-3.919045000 1.649435000 1 2.880310000-3.416882000 0.437662000 6 0.610662000 3.688590000 1.403307000 1-0.089534000 4.422843000 0.988848000 1 0.767171000 3.892313000 2.464363000 1 1.557809000 3.784058000 0.863407000 6-0.037316000 2.747142000-1.328353000 1-0.634228000 3.647247000-1.155500000 1 1.014271000 3.025209000-1.419077000 1-0.360379000 2.310228000-2.279400000 Zero-point correction= 0.307979 (Hartree/Particle) Thermal correction to Energy= 0.329756 Thermal correction to Enthalpy= 0.330701 Thermal correction to Gibbs Free Energy= 0.256826 Sum of electronic and zero-point Energies= -1087.569781 Sum of electronic and thermal Energies= -1087.548004 Sum of electronic and thermal Enthalpies= -1087.547059 Sum of electronic and thermal Free Energies= -1087.620934 TS2 6-3.752139000 0.593294000 1.150232000 6-4.365670000 0.194262000-0.038689000 6-3.578974000-0.051727000-1.163038000 6-2.204720000 0.093633000-1.075354000 7-1.636679000 0.471540000 0.088390000 6-2.378076000 0.733181000 1.184989000 6-0.197702000 0.752942000 0.120737000 6 0.048351000 2.197415000-0.136294000 6 0.689541000-0.223693000 0.371684000 6 2.147216000 0.084161000 0.508765000 8-0.835030000 3.035987000-0.126765000 8 1.338653000 2.471952000-0.384120000 8 2.644239000 0.548031000 1.513105000
S1 3 8 2.838665000-0.329337000-0.568928000 6 0.225482000-2.387122000-0.807042000 8 0.036723000-1.766348000-1.847565000 6 0.221255000-1.704337000 0.604520000 8-1.068121000-1.801831000 0.942358000 1-4.327363000 0.789911000 2.047499000 1-5.444010000 0.077793000-0.086113000 1-4.015323000-0.370976000-2.102441000 1-1.511957000-0.144416000-1.872513000 1-1.827265000 1.030416000 2.066170000 6 1.651926000 3.864323000-0.560222000 1 2.728505000 3.898497000-0.725493000 1 1.114561000 4.269215000-1.421354000 1 1.381194000 4.432214000 0.333285000 6 4.263586000-0.158493000-0.483195000 1 4.658845000-0.547188000-1.421832000 1 4.514684000 0.899289000-0.367885000 1 4.667291000-0.715201000 0.366693000 6 0.221359000-3.906411000-0.799330000 1-0.082276000-4.268367000-1.784714000 1 1.220279000-4.295637000-0.566457000 1-0.470583000-4.267577000-0.033917000 6 1.179288000-2.370127000 1.628348000 1 0.829612000-3.388945000 1.809854000 1 2.227088000-2.408816000 1.301902000 1 1.128099000-1.826426000 2.577244000 Zero-point correction= 0.304522 (Hartree/Particle) Thermal correction to Energy= 0.326798 Thermal correction to Enthalpy= 0.327742 Thermal correction to Gibbs Free Energy= 0.252383 Sum of electronic and zero-point Energies= -1087.525973 Sum of electronic and thermal Energies= -1087.503696 Sum of electronic and thermal Enthalpies= -1087.502752 Sum of electronic and thermal Free Energies= -1087.578112 Compound 17 6 3.848074000 1.211115000-0.484091000 6 4.186109000 0.307561000-1.490522000 6 3.155436000-0.478020000-2.006162000 6 1.867812000-0.352337000-1.528770000 7 1.537050000 0.530549000-0.527394000 6 2.553255000 1.309164000-0.014456000 6 0.214755000 0.612711000-0.050590000 6-0.212675000 1.767173000 0.683761000 6-0.767593000-0.426178000-0.416729000 6-1.950086000 0.059136000-1.204846000 8 0.424464000 2.775687000 0.990251000 8-1.529992000 1.625109000 1.075068000
S1 4 8-1.875819000 0.911433000-2.065045000 8-3.117192000-0.534113000-0.855247000 6 0.783884000-1.797668000 1.899440000 8 1.906728000-1.902738000 2.314866000 6-0.608662000-1.734973000-0.097049000 8 0.552630000-2.117499000 0.568402000 6-4.268164000-0.076737000-1.583583000 6-1.408828000-2.929679000-0.516146000 6-0.422861000-1.432560000 2.733962000 6-2.089214000 2.768266000 1.728307000 1 4.594560000 1.855517000-0.031225000 1 5.203092000 0.219073000-1.856318000 1 3.333850000-1.197392000-2.798713000 1 1.047187000-0.924067000-1.931796000 1 2.252970000 2.004878000 0.752580000 1-5.110429000-0.642344000-1.183296000 1-4.414661000 0.995097000-1.427600000 1-4.151707000-0.264690000-2.654481000 1-0.750886000-3.644597000-1.026464000 1-1.811201000-3.445291000 0.365642000 1-2.238621000-2.665454000-1.168292000 1-0.908029000-0.524584000 2.367038000 1-1.162499000-2.240904000 2.703396000 1-0.089005000-1.285684000 3.761714000 1-3.111847000 2.485381000 1.984551000 1-1.524814000 3.019636000 2.630576000 1-2.091310000 3.636705000 1.062935000 Zero-point correction= 0.306556 (Hartree/Particle) Thermal correction to Energy= 0.329403 Thermal correction to Enthalpy= 0.330347 Thermal correction to Gibbs Free Energy= 0.252251 Sum of electronic and zero-point Energies= -1087.581923 Sum of electronic and thermal Energies= -1087.559076 Sum of electronic and thermal Enthalpies= -1087.558132 Sum of electronic and thermal Free Energies= -1087.636228 TS3 6 2.498986000-2.613157000-0.513980000 6 3.746993000-1.999618000-0.668757000 6 3.801558000-0.612428000-0.665470000 6 2.641541000 0.131278000-0.493726000 7 1.428913000-0.477351000-0.374989000 6 1.367069000-1.839356000-0.374724000 6 0.253239000 0.329887000-0.128405000 6 0.076273000 1.391845000-1.130962000 8 0.935451000 1.845991000-1.874693000 8-1.193105000 1.880818000-1.113927000 1 2.393435000-3.692496000-0.518623000 1 4.647489000-2.593872000-0.786697000
S1 5 1 4.741031000-0.081277000-0.769954000 1 2.636822000 1.205455000-0.479616000 1 0.378441000-2.261020000-0.288148000 6-1.443096000 2.945215000-2.040514000 1-2.488276000 3.220131000-1.891539000 1-0.789711000 3.799122000-1.839598000 1-1.278630000 2.609149000-3.067719000 6 0.152348000 2.581367000 1.699900000 1 0.729184000 3.235870000 1.040877000 1-0.883673000 2.541422000 1.360054000 1 0.182724000 2.997382000 2.714077000 6-0.939107000-0.373545000 0.409169000 6-1.870063000-1.005341000-0.534908000 8-1.564202000-1.305204000-1.680034000 8-3.121223000-1.223642000-0.046121000 6 0.808380000 1.212452000 1.737932000 6-1.038265000-0.355397000 1.775647000 8-0.103166000 0.279078000 2.482337000 6-4.030363000-1.847064000-0.964620000 6-2.060331000-1.004896000 2.660474000 8 2.006016000 1.043567000 1.907304000 1-4.973630000-1.938638000-0.424129000 1-4.158007000-1.229875000-1.857612000 1-3.665354000-2.832400000-1.268345000 1-1.551388000-1.448578000 3.522159000 1-2.750032000-0.243493000 3.045284000 1-2.641945000-1.757744000 2.133176000 Zero-point correction= 0.306454 (Hartree/Particle) Thermal correction to Energy= 0.328170 Thermal correction to Enthalpy= 0.329114 Thermal correction to Gibbs Free Energy= 0.255518 Sum of electronic and zero-point Energies= -1087.578295 Sum of electronic and thermal Energies= -1087.556579 Sum of electronic and thermal Enthalpies= -1087.555635 Sum of electronic and thermal Free Energies= -1087.629231 Compound 18 6-3.579748000-1.126116000 0.031476000 6-3.679026000-1.413883000-1.327044000 6-2.637884000-1.025959000-2.169318000 6-1.550912000-0.345262000-1.648443000 7-1.489016000-0.038093000-0.327230000 6-2.476175000-0.438306000 0.513040000 6-0.194833000 0.574466000 0.245062000 6 0.307838000 1.637078000-0.764172000 6 0.765622000-0.540489000 0.533087000 6 1.585216000-0.961214000-0.566013000 8-0.351076000 2.115392000-1.661125000 8 1.526803000 2.064823000-0.412652000
S1 6 8 1.497421000-0.510227000-1.718425000 8 2.505571000-1.926969000-0.274618000 6-0.567975000 1.460381000 1.500000000 8-1.690269000 1.918524000 1.599124000 6 0.558600000-1.178830000 1.790079000 8-0.356452000-0.765974000 2.551777000 1-4.347872000-1.428131000 0.734374000 1-4.541579000-1.943598000-1.720047000 1-2.651295000-1.248744000-3.230242000 1-0.697683000-0.065562000-2.244716000 1-2.331767000-0.228163000 1.558507000 6 2.105162000 3.045750000-1.291402000 1 3.065392000 3.302534000-0.844116000 1 2.245772000 2.610670000-2.283796000 1 1.461981000 3.926105000-1.364716000 6 0.555315000 1.920747000 2.407144000 1 0.230043000 1.769579000 3.438738000 1 1.493466000 1.398142000 2.230709000 1 0.704271000 2.994553000 2.248101000 6 1.397609000-2.352165000 2.269207000 1 1.046824000-2.633860000 3.264519000 1 1.312020000-3.206438000 1.590446000 1 2.459602000-2.091602000 2.307336000 6 3.306451000-2.359501000-1.377687000 1 3.966824000-3.129170000-0.973736000 1 2.686038000-2.773063000-2.178391000 1 3.893517000-1.531336000-1.785087000 Zero-point correction= 0.307163 (Hartree/Particle) Thermal correction to Energy= 0.329441 Thermal correction to Enthalpy= 0.330385 Thermal correction to Gibbs Free Energy= 0.256088 Sum of electronic and zero-point Energies= -1087.590009 Sum of electronic and thermal Energies= -1087.567731 Sum of electronic and thermal Enthalpies= -1087.566787 Sum of electronic and thermal Free Energies= -1087.641084 TS4 6 3.544311000-0.563982000-1.421945000 6 4.452277000 0.042394000-0.568416000 6 3.960348000 0.866054000 0.455232000 6 2.604989000 1.053464000 0.595927000 7 1.716259000 0.474102000-0.267257000 6 2.181468000-0.352575000-1.246316000 6 0.301997000 0.608611000-0.100397000 6-0.152807000 1.921406000 0.352758000 6-0.527485000-0.489104000-0.348632000 6-1.948821000-0.270253000-0.742271000 8 0.536748000 2.930052000 0.439632000 8-1.464472000 1.913358000 0.708537000
S1 7 8-2.932070000-0.825539000-0.283780000 8-2.025987000 0.600951000-1.776982000 6-0.688928000-1.558629000 1.685907000 8-0.028260000-0.853334000 2.373747000 6-0.033051000-1.888034000-0.182790000 8 1.198101000-2.123276000 0.030530000 6-3.357033000 0.905369000-2.216023000 6-1.990735000 3.179223000 1.123741000 6-1.751167000-2.535255000 2.111732000 6-0.838070000-3.021663000-0.830277000 1 3.865509000-1.209854000-2.231282000 1 5.519669000-0.112220000-0.689894000 1 4.627219000 1.354383000 1.156949000 1 2.174061000 1.656634000 1.378232000 1 1.442811000-0.694613000-1.954554000 1-3.238102000 1.615624000-3.035253000 1-3.868321000 0.002654000-2.561378000 1-3.936492000 1.350530000-1.402321000 1-3.034199000 2.989611000 1.378883000 1-1.446371000 3.555801000 1.993798000 1-1.919752000 3.915205000 0.317619000 1-1.449911000-3.550392000 1.837836000 1-1.891481000-2.468657000 3.195135000 1-2.673449000-2.293726000 1.578625000 1-0.537403000-3.965232000-0.366598000 1-1.920749000-2.906165000-0.781355000 1-0.543101000-3.078143000-1.886493000 Zero-point correction= 0.304225 (Hartree/Particle) Thermal correction to Energy= 0.326563 Thermal correction to Enthalpy= 0.327508 Thermal correction to Gibbs Free Energy= 0.253197 Sum of electronic and zero-point Energies= -1087.526534 Sum of electronic and thermal Energies= -1087.504196 Sum of electronic and thermal Enthalpies= -1087.503252 Sum of electronic and thermal Free Energies= -1087.577563 Compound 20 6-3.452556000-1.237787000 0.581150000 6-4.426866000-0.326877000 0.174640000 6-3.984650000 0.894283000-0.336153000 6-2.636978000 1.169048000-0.454305000 7-1.677777000 0.273044000-0.040280000 6-2.113384000-0.917203000 0.486912000 6-0.310053000 0.577414000-0.150089000 6 0.073146000 1.929477000 0.105050000 6 0.727541000-0.508485000-0.336566000 6 1.337926000-1.045623000 0.967749000 8-0.644135000 2.923287000 0.232356000 8 1.444986000 2.038242000 0.252298000
S1 8 8 2.307299000-1.775135000 1.045110000 8 0.647837000-0.644907000 2.056113000 6 1.872892000 0.077292000-1.321996000 8 1.513653000 0.491764000-2.396831000 6 0.216474000-1.700248000-1.240496000 8-0.739101000-1.533172000-1.963826000 6 1.171589000-1.094291000 3.318150000 6 1.931896000 3.376340000 0.385372000 6 3.335877000 0.016482000-0.937305000 6 0.978261000-3.012330000-1.240480000 1-3.719051000-2.201371000 1.003177000 1-5.483593000-0.558428000 0.251866000 1-4.685409000 1.646702000-0.682891000 1-2.257996000 2.089037000-0.866336000 1-1.346190000-1.570605000 0.869279000 1 0.500998000-0.682587000 4.072404000 1 1.185029000-2.186546000 3.364449000 1 2.188433000-0.720503000 3.461330000 1 3.018123000 3.288426000 0.453337000 1 1.653888000 3.982313000-0.481744000 1 1.531440000 3.848199000 1.286756000 1 3.694303000-1.017123000-0.941666000 1 3.891391000 0.599874000-1.674666000 1 3.504351000 0.410540000 0.066046000 1 0.559535000-3.640973000-2.028473000 1 2.048554000-2.861760000-1.407196000 1 0.889636000-3.522086000-0.275261000 Zero-point correction= 0.305430 (Hartree/Particle) Thermal correction to Energy= 0.328290 Thermal correction to Enthalpy= 0.329235 Thermal correction to Gibbs Free Energy= 0.252120 Sum of electronic and zero-point Energies= -1087.562890 Sum of electronic and thermal Energies= -1087.540029 Sum of electronic and thermal Enthalpies= -1087.539085 Sum of electronic and thermal Free Energies= -1087.616200 TS5 6 3.226986000-0.361910000-1.791582000 6 4.236752000 0.099818000-0.943077000 6 3.894426000 0.659840000 0.284435000 6 2.557664000 0.749598000 0.643540000 7 1.596332000 0.308795000-0.199946000 6 1.911153000-0.261301000-1.385424000 6 0.209872000 0.429134000 0.216826000 6-0.275403000 1.793982000-0.102266000 6-0.627949000-0.845360000 0.273575000 6-2.061665000-0.744622000-0.172409000 8 0.466865000 2.727467000-0.362758000 8-1.617371000 1.931132000-0.012531000
S1 9 8-3.047862000-0.968831000 0.495053000 8-2.121080000-0.449798000-1.499479000 6-0.040134000-0.189396000 1.746264000 8 0.970067000-0.694854000 2.285801000 6-0.054242000-2.199904000 0.075507000 8 1.146710000-2.408161000-0.065790000 6-3.445987000-0.308137000-2.033624000 6-2.109603000 3.269364000-0.189555000 6-1.113084000 0.464387000 2.606940000 6-1.027213000-3.369821000 0.151261000 1 3.452059000-0.805334000-2.754501000 1 5.278267000 0.023861000-1.240337000 1 4.649119000 1.027329000 0.970033000 1 2.215938000 1.153391000 1.582330000 1 1.073079000-0.584266000-1.986948000 1-3.314774000-0.076137000-3.091453000 1-4.014495000-1.233852000-1.910677000 1-3.976157000 0.502419000-1.525888000 1-3.187869000 3.201897000-0.042699000 1-1.662442000 3.944387000 0.544373000 1-1.877967000 3.632162000-1.194205000 1-1.427158000-0.281032000 3.343709000 1-0.662489000 1.301098000 3.154468000 1-1.989881000 0.808923000 2.063748000 1-0.444645000-4.290892000 0.213896000 1-1.693978000-3.284577000 1.014255000 1-1.658996000-3.410615000-0.745334000 Zero-point correction= 0.304751 (Hartree/Particle) Thermal correction to Energy= 0.326938 Thermal correction to Enthalpy= 0.327882 Thermal correction to Gibbs Free Energy= 0.253674 Sum of electronic and zero-point Energies= -1087.538301 Sum of electronic and thermal Energies= -1087.516114 Sum of electronic and thermal Enthalpies= -1087.515170 Sum of electronic and thermal Free Energies= -1087.589378 Compound 19 6 1.563311000 1.629072000-0.075099000 6 0.709664000 0.365933000 0.048566000 6-0.638118000 0.362263000-0.003991000 6-1.365011000 1.684508000-0.134241000 6-2.598301000 1.784093000-1.009147000 8 1.745969000 2.103261000-1.176241000 8-0.913377000 2.669365000 0.425545000 6 1.541756000-0.878899000 0.239117000 6-1.359478000-0.942701000 0.116031000 8 1.966167000-1.211509000 1.324337000 8 1.843451000-1.451405000-0.929046000 6 2.623872000-2.659684000-0.837589000
S2 0 8-0.823742000-2.033118000 0.128461000 8-2.689706000-0.775241000 0.263586000 6-3.449088000-1.986529000 0.433886000 6 2.181943000 2.143751000 1.199179000 1-3.488820000 1.530893000-0.425283000 1-2.556358000 1.097924000-1.860158000 1-2.684502000 2.815984000-1.356850000 1 2.814226000-2.958140000-1.868141000 1 2.052275000-3.427725000-0.311025000 1 3.560720000-2.471542000-0.307840000 1-4.485106000-1.665841000 0.542238000 1-3.113453000-2.521582000 1.325426000 1-3.333149000-2.634871000-0.438123000 1 2.937322000 2.896932000 0.963456000 1 2.617239000 1.323131000 1.779613000 1 1.386202000 2.593157000 1.803282000 Zero-point correction= 0.213185 (Hartree/Particle) Thermal correction to Energy= 0.231619 Thermal correction to Enthalpy= 0.232563 Thermal correction to Gibbs Free Energy= 0.164739 Sum of electronic and zero-point Energies= -839.398388 Sum of electronic and thermal Energies= -839.379954 Sum of electronic and thermal Enthalpies= -839.379009 Sum of electronic and thermal Free Energies= -839.446834