S1

A Theoretical Study of the Duff Reaction: Insights into its Selectivity

Nicolás Grimblat,* Ariel M. Sarotti, Teodoro S. Kaufman, and Sebastian O. Simonetti*

Instituto de Química Rosario (CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina

Supporting Information

List of contents:

x Computational methods with full list of authors in the Gaussian 09 reference. Page S2.

x Experimental Procedure for the Duff formylation of the 3-methylphenol 1H NMR. Page S3.

x 1H NMR of the mixture of 2-hydroxy-4-methylbenzaldehyde and 2-hydroxy-6-methylbenzaldehyde. Page S4.

x 13C NMR of the mixture of 2-hydroxy-4-methylbenzaldehyde and 2-hydroxy-6-methylbenzaldehyde. Page S5

x Reaction coordinates for phenols not included in the paper. Page S6-S8

x References of the Supporting Information. Page S9

x Cartesian coordinates, absolute energies including zero-point energy corrections, free energies in solution and number of imaginary frequencies of all the stationary points reported in the paper; values of imaginary frequencies of all transition structures. Pages S10-S32.

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016

S2

Computational methods

Conformational searches for the reactants, the transition structures (TSs) and the products were run to locate the global minima employing the M06-2X functional1 coupled with the 6-311+G(d,p) level of theory. Initially, a large number of geometries were generated using the conformational search module of Hyperchem2 with the MM+ method for the TSs and Spartan’s conformer distribution module employing MMFF was employed for both reactants and products.3 Selected structures were then optimized at the M06-2X/6-311+G** level of theory using Gaussian 09.4 Geometries for all structures were fully optimized including Acetic Acid (ε=6.2528) as solvent using SMD.5 Reported thermochemical properties include zero-point energies (ZPEs) without scaling and were calculated at 1 atm and the corresponding temperature for each reaction.6 Normal mode analysis was used to confirm the nature of the stationary points and to evaluate the thermochemical properties. All transition structures were confirmed to have only one imaginary frequency corresponding to the formation of the expected bonds. Intrinsic reaction coordinate (IRCs) calculations were run to verify the connectivity between reactants, TSs and products.

S3

Fig S1. Spectrum of 1H of 2-hydroxy-4-methylbenzaldehyde and 2-hydroxy-6-methylbenzaldehyde (300 MHz in CDCl3).

S4

Fig S2. Spectrum of 13C of 2-hydroxy-4-methylbenzaldehyde and 2-hydroxy-6-methylbenzaldehyde (75 MHz in CDCl3).

S5

Reactioncoordinatesforphenolsnotincludedinthepaper

P-2+HMTA+-R6

TS-2+HMTA+-R6ΔG≠ 20.03

ΔG 6.03

ΔG 13.90

TS-2+HMTA+-R2

ΔG≠ 17.73

2 + HMTA+

P-2+HMTA+-R2

P-3+HMTA+-R6

TS-3+HMTA+-R6 ΔG≠ 20.22

ΔG 11.08

ΔG 1.50

TS-3+HMTA+-R2

ΔG≠ 24.36

3 + HMTA+ P-3+HMTA+-R2

P-4+HMTA+-R6

TS-4+HMTA+-R6

ΔG≠ 19.93

ΔG 4.99

ΔG 11.68

TS-4+HMTA+-R2ΔG≠ 17.61

4 + HMTA+ P-4+HMTA+-R2

S6

FigureS3.Reactioncoordinatesforthephenolderivativesnotincludedinthemanuscript

P-6+HMTA+-R6

TS-6+HMTA+-R6ΔG≠ 24.42

ΔG 12.38

ΔG 15.05

TS-6+HMTA+-R2ΔG≠ 22.31

6 + HMTA+ P-6+HMTA+-R2

P-7+HMTA+-R6

TS-7+HMTA+-R6ΔG≠ 20.63

ΔG 9.50

ΔG 7.71

TS-7+HMTA+-R2

ΔG≠ 19.88

7 + HMTA+

P-7+HMTA+-R2

S7

References

(1) (a)Y.ZhaoandD.G.Truhlar,Theor.Chem.Acc.2008,120,215;(b)Y.Zhao,D.G.Truhlar,Acc.Chem.Res.2008,41,157.(2) HyperchemProfessionalRelease7.52;Hypercube,Inc.,2005.(3) Spartan’08;Wavefunction:Irvine,CA.(4) M.J.T.Frisch,G.W.;H.B.Schlegel,G.E.Scuseria,M.A.Robb,J.R.Cheeseman,G.Scalmani,V.Barone,B.Mennucci,G.A.Petersson,H.Nakatsuji,M.Caricato,X.Li,H.P.Hratchian,;A.F.Izmaylov,J.Bloino,G.Zheng,J.L.Sonnenberg,M.Hada,M.Ehara,K.Toyota,R.Fukuda,J.Hasegawa,M.Ishida,T.Nakajima,Y.Honda,O.Kitao,H.Nakai,T.Vreven,J.A.MontgomeryJr.,J.E.Peralta,F.Ogliaro,M.Bearpark,J.J.Heyd,E.Brothers,K.N.Kudin,V.N.Staroverov,T.Keith,R.Kobayashi,J.Normand,K.Raghavachari,A.Rendell,J.C.Burant,S.S.Iyengar,J.Tomasi,M.Cossi,N.Rega,N.J.Millam,M.Klene,J.E.Knox,J.B.Cross,V.Bakken,C.Adamo,J.Jaramillo,R.Gomperts,R.E.Stratmann,O.Yazyev,A.J.Austin,R.Cammi,C.Pomelli,J.W.Ochterski,R.L.Martin,K.Morokuma,V.G.Zakrzewski,G.A.Voth,P.Salvador,J.J.Dannenberg,S.Dapprich,A.D.Daniels,Ö.Farkas,J.B.Foresman,J.V.Ortiz,J.Cioslowski,D.J.Fox,Gaussian,Inc.:WallingfordCT,2010.(5) A.V.Marenich,C.J.CramerandD.G.Truhlar,J.Phys.Chem.B2009,113,6378.(6) Temperaturesemployedforeachphenol:1-110ºC;2-90ºC;3-100ºC;4-70ºC;5-75ºC;6-140ºC;7-110ºC;8-110ºC(7) (a)W.Shen,J.Mao,J.Sun,;M.SunandC.Zhang,Med.Chem.Res.2012,22,1630;(b)R.J.Bergeron,J.Wiegand,J.S.McManis,N.BhartiandS.J.Singh,Med.Chem.2008,51,5993;c)P.A.Plé,T.P.Green,L.F.Hennequin,J.Curwen,M.Fennell,J.Allen,C.Lambert-vanderBremptandG.Costello,J.Med.Chem.2004,47,871;d)M.Inouye,K.AkamatsuandH.Nakazumi,J.Am.Chem.Soc.1997,119,9160;e)A.Ishikawa,Y.Kato,K.Tamura,Y.TakashimaandO.Cynshi,US2002/0156296:2002;f)Q.Li,K.W.Woods,W.Wang,N.-H.Lin,A.Claiborne,W.-Z.Gu,J.Cohen,V.S.Stoll,C.Hutchins,D.Frost,S.H.RosenbergandH.L.Sham,Bioorg.Med.Chem.Lett.2005,15,2033;g)D.Mal,A.PatraandH.Roy,TetrahedronLett.2004,45,7895;h)S.O.Simonetti,E.L.LarghiandT.S.Kaufman,Org.Biomol.Chem.2016,14,2625;i)Y.O.T.Hoyano,Y.Kai,N.Kikuchi,H.Kobayashi,H.Mukaiyama,K.Okazaki,H.Shiohara,H.M.Takecuchi,Y.F.TeraoandM.Uchida,EP1331221(A1):2003;j)F.Dallacker,G.ReichrathandG.Z.Schnackers,Naturforsc.B1979,34,624;k)J.J.Talley,E.J.MartínezandJerome,K.D.;US2015/197500(A1):2015;l)J.C.DuffandV.I.Furness,J.Chem.Soc.1951,1512;m)X.-W.Fu,W.-C.Pu,G.-l.ZhangandC.Wang,Res.Chem.Intermed.2014,41,8147;n)T.Seki,T.Nakao,T.Masuda,K.Hasumi,K.Gotanda,T.Ishimori,S.Honma,N.Minami,K.ShibataandK.Yasuda,Chem.Pharm.Bull.1996,44,2061;o)C.Gleye,G.Lewin,A.Laurens,J.-C.Jullian,P.Loiseau,C.BoriesandR.Hocquemiller,J.Nat.Prod.2003,66,690.(8) F.Yang,K.Rauch,K.KettelhoitandL.Acherman,Angew.Chem.Int.Ed.2014,53,11285-11288.

S8

CARTESIAN COORDINATES, ABSOLUTE ENERGIES INCLUDING ZERO-POINT ENERGY CORRECTIONS, FREE ENERGIES IN SOLUTION AND NUMBER OF IMAGINARY FREQUENCIES OF ALL THE STATIONARY POINTS REPORTED IN THE PAPER; VALUES OF IMAGINARY FREQUENCIES OF ALL TRANSITION STRUCTURES. REACTANTS1RM062X/6-311+G(d,p)(AceticAcid)01O2.390859-1.0465630.001086C1.218378-0.3418110.000580C-1.1050451.177018-0.004251C1.3105041.0489020.003680C-0.021670-0.970179-0.005124C-1.197514-0.214483-0.006074C0.1427791.7986980.001137C-2.533433-0.9095390.004667H2.208159-1.993661-0.001791H-2.0095851.775475-0.007677H2.2883761.5164870.006200H-0.070806-2.055972-0.008889H0.2054782.8813630.001638H-2.703983-1.4035690.965555H-3.346543-0.201349-0.160670H-2.581960-1.677898-0.770746NUMBEROFIMAGINARYFREQUENCIES=0ZPEENERGY=-346.608227FREEENERGY=-346.6521872RM062X/6-311+G(d,p)(AceticAcid)01O0.6891412.885990-0.007059C0.6872221.654131-0.008509C1.871679-0.482420-0.020358C-0.484132-0.524793-0.011824O0.710430-1.180838-0.022962C-0.5515900.869006-0.005508C1.9041850.866038-0.011741C-1.8194401.4681590.006677C-2.9639490.7033030.013742C-2.859412-0.6986090.008233C-1.622787-1.322241-0.005054O-3.956646-1.4941930.015599C3.042223-1.410109-0.033227C4.397690-0.7264620.062426H2.8526041.386279-0.009089H-1.8808722.5502810.011094

H-3.9454861.1644590.024070H-1.539809-2.402079-0.008796H-4.761394-0.9607210.025340H2.904758-2.1142680.793905H2.972950-2.003310-0.951742H4.486507-0.1483500.984932H5.187418-1.4792880.059304H4.569783-0.056687-0.782791NUMBEROFIMAGINARYFREQUENCIES=0ZPEENERGY=-650.611154FREEENERGY=-650.6604453RM062X/6-311+G(d,p)(AceticAcid)01O3.119063-0.7095650.036503C1.847329-0.2023010.009826C-0.7290150.729951-0.034685C0.807702-1.143758-0.026935C1.5977101.1650200.022731C0.2829921.655858-0.003189C-0.467900-0.634612-0.045855O-1.653577-1.319115-0.122102C-2.651504-0.3448760.197832O-2.0923680.925855-0.120876H3.7608780.0102990.059077H1.013921-2.206443-0.040782H2.4321671.8567590.055492H0.0794922.719308-0.002805H-3.536011-0.517873-0.409400H-2.859273-0.3911431.271868Numberofimaginaryfrequencies=0ZPEEnergy=-495.832896FreeEnergy=-495.8769024RM062X/6-311+G(d,p)(AceticAcid)01N-1.4565661.254126-0.000008C-0.1229280.862013-0.000007C2.446489-0.1971360.000005C0.9753951.723566-0.000008C0.093875-0.526530-0.000005

S9

C1.372662-1.0759630.000003C2.2529571.192846-0.000002S-1.445520-1.339320-0.000014C-2.2466010.239421-0.000012C-3.7350960.3110260.000027O3.698083-0.7454270.000015H0.8186152.795947-0.000014H1.547288-2.1450950.000007H3.1185601.846868-0.000003H-4.145962-0.182693-0.883613H-4.0413751.356731-0.000034H-4.145883-0.1825570.883781H4.367875-0.0510030.000019NUMBEROFIMAGINARYFREQUENCIES=0ZPEENERGY=-837.056469FREEENERGY=-837.0982535RM062X/6-311+G(d,p)(AceticAcid)01O2.709210-1.902696-0.009508C2.023828-0.723442-0.003594C0.5235341.6257650.005403C0.634896-0.796757-0.013565C2.6657670.5124480.013283C1.9107971.6812640.017510C-0.1072800.381524-0.009059C-1.5968850.353152-0.013509O-2.2906851.344993-0.030110O-2.098183-0.8800290.008400C-3.529152-0.9781880.024558H3.659567-1.737019-0.000363H-0.0723172.5301790.008888H0.154288-1.767246-0.025561H3.7502730.5534070.022972H2.4155402.6401170.031628H-3.747988-2.0423490.062529H-3.946166-0.536462-0.880981H-3.928969-0.4733680.904460Numberofimaginaryfrequencies=0ZPEEnergy=-535.148366FreeEnergy=-535.1934806RM062X/6-311+G(d,p)(AceticAcid)01O4.0091401.018284-0.102977

C2.8075730.381939-0.084309C0.289372-0.800215-0.032326C2.682181-0.997918-0.217937C1.6732841.1691540.078027C0.4106600.5849780.086201C1.424949-1.586589-0.177596C-0.7471051.5200210.240232O-0.8045292.3658041.100810O-1.6675661.355562-0.697042C-2.8109892.221228-0.616453Br-1.394449-1.6712540.125469H4.7279960.385320-0.221905H3.566588-1.614273-0.339967H1.7748002.2433310.186996H1.336203-2.663617-0.251927H-3.3401262.0532950.322264H-2.4966793.262909-0.685801H-3.4389511.954142-1.462432Numberofimaginaryfrequencies=0ZPEEnergy=-3108.723170FreeEnergy=-3108.7836557RM062X/6-311+G(d,p)(AceticAcid)01O-3.407290-0.4408630.000000C-2.039510-0.4673950.000000C0.762512-0.3872620.000000C-1.3824250.7602040.000000C-1.307010-1.6451870.000000C0.085859-1.6035140.000000C0.0000000.7879070.000000Cl0.8168922.3282720.000000O2.113772-0.2548650.000000C2.888197-1.4465110.000000H-3.755113-1.3404460.000000H-1.9545521.6800670.000000H-1.819999-2.6008550.000000H0.638019-2.5340880.000000H3.927667-1.1248490.000000H2.689608-2.0420350.895445H2.689608-2.042035-0.895445Numberofimaginaryfrequencies=0ZPEEnergy=-881.414913FreeEnergy=-881.4626018RM062X/6-311+G(d,p)(AceticAcid)

S10

01O1.217476-3.0803150.000000C0.265965-2.0954980.000000C-1.557143-0.0046190.000000C0.713983-0.7804720.000000C-1.097582-2.3823340.000000C-1.998790-1.3266380.000000C-0.1894140.2870260.000000C0.3544881.7179570.000000C1.2174761.9335801.253204C1.2174761.933580-1.253204C-0.7638552.7617990.000000H0.798678-3.9493260.000000H-2.2916250.7901950.000000H1.785198-0.6094970.000000H-1.437357-3.4129890.000000H-3.062949-1.5360110.000000H0.6310161.7749642.163037H2.0730441.2542691.277946H1.6017222.9579881.269949H1.6017222.957988-1.269949H0.6310161.774964-2.163037H2.0730441.254269-1.277946H-1.3979482.6785200.887010H-1.3979482.678520-0.887010H-0.3230453.7623740.000000Numberofimaginaryfrequencies=0ZPEEnergy=-464.437659FreeEnergy=-464.487023HTMA+RM062X/6-311+G(d,p)(AceticAcid)11C2.440045-0.000006-0.796391C-1.260906-1.208440-0.667630C0.853888-1.2732390.551550C0.8538881.2732450.551546C-0.9660240.0000121.376079C-1.2608981.208435-0.667653H-0.923917-2.070954-1.242065H2.8552870.944020-1.138828H-2.0482830.0000141.503415H-2.324404-1.329558-0.449219H-0.4886940.0000242.357822H2.855280-0.944037-1.138824H1.279437-1.3898481.550554H1.180576-2.085248-0.097778H1.1805902.085253-0.097775

H1.2794201.3898491.550558H-2.3243971.329567-0.449252H-0.9238952.070934-1.242101N1.463067-0.0000020.009902N-1.086322-0.000011-1.463252N-0.5717671.2019510.636905N-0.571769-1.2019430.636925H-0.189426-0.000018-1.934885Numberofimaginaryfrequencies=0ZPEEnergy=-454.999722FreeEnergy=-455.044126TransitionStatesTS-1+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C0.7179230.894967-0.969541C-2.7535610.7277181.389134C-1.4510861.779163-0.387623C-1.204709-0.499648-1.507111C-3.3269020.417188-0.907460C-2.582228-1.5098860.255467H-2.2094161.3444662.102352H1.3012000.249667-1.619895H-4.3427630.160142-0.606447H-3.7887630.6122161.711731H-3.3508210.912526-1.878817H1.0640741.908454-0.798804H-1.6131712.437899-1.244586H-0.9286192.3232050.399460H-0.537303-1.354390-1.391353H-1.303298-0.250198-2.567006H-3.614287-1.8045680.446459H-1.933886-2.3837320.245004N-0.5657340.670709-0.839394N-2.137576-0.6501921.416700N-2.523999-0.801521-0.995827N-2.7364531.3221520.078833H-2.411434-1.1130702.287768C1.9242410.3017110.820699C3.889702-0.190030-0.481250C3.379108-1.487686-0.712806C2.192801-1.907308-0.161171C1.428350-1.0263640.664928O0.308529-1.3863191.177590H4.8413000.100997-0.911693H1.818197-2.912624-0.322957C3.1899200.6917030.315435

S11

H1.4033040.9529981.518710H-1.069799-0.6604271.398633H3.947884-2.171467-1.335261C3.6911792.0787670.597998H4.6758982.2423260.158123H3.0041802.8293680.190747H3.7572002.2569451.674743Numberofimaginaryfrequencies=1(-170.5568)ZPEEnergy=-801.603025FreeEnergy=-801.662574TS-1+HMTA+-R4RM062X/6-311+G(d,p)(AceticAcid)11C1.1427611.690774-0.001633C1.3079061.4095981.388481C2.1102730.3762301.792756C2.737212-0.4569230.837292C2.751197-0.066631-0.531808C1.9487720.974427-0.931957O0.2773072.561034-0.403023H-2.5885722.291133-0.546369H0.7670962.0225722.102276H2.2136940.1422112.847929H3.428870-1.2248861.168786H1.8852671.255912-1.979113C1.023730-1.8125330.601003C-2.1560380.553748-1.568219C-0.617397-1.324135-1.101896C-1.092260-1.0488591.440191C-2.820465-1.263575-0.184565C-2.5977100.8381700.917475H-1.4221430.910140-2.290133H1.172115-2.1618571.616555H-3.856384-1.003050-0.406046H-3.1624960.689097-1.964669H-2.740520-2.342734-0.044901H1.537088-2.347897-0.190350H-0.600606-2.385489-1.361289H0.074785-0.780862-1.744449H-0.648647-0.3667312.164757H-1.219816-2.0327061.898601H-3.6714931.0277020.906054H-2.1400201.3648381.753224N-0.119827-1.2283370.312036N-2.0441411.446034-0.351608N-2.390163-0.5793801.029940N-1.963574-0.842787-1.287733

H-1.0358261.831157-0.259638C3.589239-0.839609-1.508201H3.361322-0.562739-2.538343H4.651257-0.649293-1.327045H3.437191-1.917586-1.393606Numberofimaginaryfrequencies=1(-246.8664)ZPEEnergy=-801.590128FreeEnergy=-801.649678TS-1+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.4173671.2599020.773592C2.8065690.144594-1.500880C1.8661241.7118810.113689C1.375263-0.2192571.634949C3.5533660.1851130.762869C2.407351-1.7468540.012952H2.3399460.728117-2.295117H-1.0461210.8284691.549068H4.485025-0.2916320.455494H3.784418-0.205223-1.847032H3.7465010.8343531.618486H-0.5493652.3307940.643302H2.1948112.4552920.849068H1.3959632.229272-0.725026H0.590860-0.9628411.780684H1.6181500.2405792.599407H3.369059-2.232351-0.178950H1.668627-2.5105630.259409N0.8611680.8330100.733656N1.941765-1.029641-1.207117N2.587798-0.8484511.140000N3.0338870.990146-0.342336H2.030642-1.675234-1.992465C-1.3611350.771433-0.810547C-3.7188411.055101-0.269387C-3.792312-0.3191780.126543C-2.694113-1.134316-0.013473C-1.483466-0.625233-0.532764O-0.468193-1.431927-0.644483H-4.6070881.671688-0.187543H-2.734742-2.1839760.255781C-2.5628461.563574-0.766891H-0.5829181.073338-1.506236H0.472880-1.032445-0.973371H-2.5050922.600256-1.081519C-5.083489-0.8422650.673834

S12

H-5.367386-0.2835941.570240H-5.884368-0.700375-0.057724H-5.017213-1.9009300.923559Numberofimaginaryfrequencies=1(-417.4802)ZPEEnergy=-801.599895FreeEnergy=-801.658205TS-1+HMTA+-R2(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11O-2.658888-2.325129-0.573840H-3.092527-2.151261-1.422374C-0.842442-0.049422-1.623482C2.302884-1.1422201.151798C1.098965-1.337027-0.972630C1.1800841.182584-1.158191C3.129068-0.128129-0.842890C2.4090171.2575070.955846H1.682884-1.9511081.541492H-1.0171280.830720-2.242113H4.131555-0.126976-0.412274H3.319611-1.2719961.531546H3.209104-0.221241-1.928549H-1.064921-0.972369-2.162433H1.272362-1.643497-2.012180H0.466896-2.086370-0.487328H0.6008952.028276-0.776458H1.3490301.327296-2.232641H3.4398421.3530611.306558H1.8706122.1710191.211739N0.360332-0.047018-0.970511N1.7870390.1318461.647229N2.4673781.132924-0.506971N2.379671-1.266693-0.310973H0.7936630.1647791.453998C-2.3438350.061512-0.618848C-1.6644501.1426051.438233C-1.476909-0.1404452.003423C-1.798498-1.3110851.342362C-2.311989-1.2111800.054336H-1.4454762.0223812.032190C-2.1628201.2653790.170111H-3.0562400.132621-1.440842H-1.090473-0.2081743.015747H-1.696588-2.2817701.811370C-2.4668902.586143-0.455706H-2.1115843.4078020.165872H-2.0162912.671369-1.449492

H-3.5481732.691728-0.590696Numberofimaginaryfrequencies=1(-299.0971)ZPEEnergy=-801.587399FreeEnergy=-801.647349TS-1+HMTA+-R4(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11C0.605907-1.8005290.929010C-1.9688560.592422-1.654795C-1.059496-1.509668-0.788064C-1.405221-0.6183801.569633C-3.150799-0.693000-0.030755C-2.2862961.4446300.576582H-1.2408650.541038-2.465795H0.636339-2.0111321.996265H-4.076249-0.210599-0.349039H-2.9111370.972624-2.058144H-3.378300-1.7018920.321801H0.845464-2.6744890.324752H-1.333466-2.568451-0.705360H-0.287286-1.406445-1.556058H-0.8431140.0259662.251099H-1.760307-1.4949882.124527H-3.2577631.9086630.386789H-1.7842402.0047901.366391N-0.467535-1.0834290.510712N-1.4895361.529476-0.644546N-2.5579710.0832581.058567N-2.236799-0.769567-1.172034H-0.5331051.286380-0.413825C2.280991-0.9863690.785105C1.8511961.3481281.320204C1.8055591.610785-0.067426C2.0646730.611060-1.024965C2.373959-0.663300-0.614226H1.6818772.1643102.011895C2.1430290.0828571.730998H2.837421-1.8611471.112995H2.202223-0.1486762.789339O1.5263342.860534-0.414072H1.5044152.978082-1.374821H2.0644990.876953-2.077862C2.757873-1.727774-1.589559H2.577483-1.413668-2.617567H3.821878-1.958776-1.476485H2.211335-2.656155-1.397660

S13

Numberofimaginaryfrequencies=1(-367.3597)ZPEEnergy=-801.589820FreeEnergy=-801.649642TS-1+HMTA+-R6(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11O2.697056-1.592278-1.566554H2.923441-2.464945-1.213164C0.535856-1.9488050.653508C-1.8400830.979954-1.472211C-1.037783-1.296051-1.056477C-1.526738-0.9370101.404077C-3.164717-0.605029-0.279603C-2.3308731.3107190.864421H-1.0474661.092496-2.213928H0.511523-2.3469341.666418H-4.055939-0.033122-0.541908H-2.7397091.474137-1.848632H-3.433328-1.659923-0.186684H0.786903-2.708667-0.088484H-1.345854-2.338258-1.208838H-0.218812-1.069186-1.745013H-1.011795-0.4740342.250292H-1.915940-1.9129571.717965H-3.2811991.8279990.707523H-1.8933251.6658921.798565N-0.520451-1.1545290.329206N-1.4343191.645480-0.237568N-2.645598-0.1177781.000310N-2.168330-0.447059-1.340221H-0.5040891.3253770.005024C2.198697-1.1581230.747468C1.8411051.1594141.389131C1.8904101.5373610.014141C2.1541550.594345-0.969642C2.391103-0.726356-0.606739H1.6676561.9254862.136347C2.046605-0.1350921.748833H2.734733-2.0596061.037930H2.2276430.880210-2.012935H2.032325-0.4366022.790730C1.7201382.977292-0.349865H2.6912003.476941-0.250883H1.3823333.097830-1.379260H1.0268793.4775720.327020Numberofimaginaryfrequencies=1(-372.6181)

ZPEEnergy=-801.587259FreeEnergy=-801.646695TS-2+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.461702-0.3395891.020511C-3.845726-1.379440-1.231656C-2.279287-1.8640650.580007C-2.7117450.4613361.532682C-4.471963-1.0766081.048693C-4.3204040.896125-0.265155H-3.153208-1.863849-1.918013H-0.0944010.5192051.575353H-5.518572-1.1508500.752586H-4.873644-1.590293-1.528057H-4.349747-1.4805452.054219H0.166687-1.2232100.970209H-2.236499-2.4768011.484016H-1.622016-2.288986-0.179759H-2.3271041.4653721.351243H-2.7329190.2616422.607307H-5.3933090.873715-0.455540H-3.9440591.915055-0.330006N-1.758893-0.5136800.926384N-3.6567320.112928-1.377712N-4.0602120.3264761.028982N-3.644746-1.8416840.115678H-4.0659460.406237-2.269607C0.4144150.287793-0.880798C2.3968701.3953770.025728C1.6476152.6048400.093341C0.3568452.678182-0.335900C-0.3068841.521883-0.884829O-1.5105981.575359-1.280448C1.7721900.280090-0.499264H0.018457-0.562452-1.426247H-2.6447300.423185-1.404340C4.389358-0.0050190.304944C3.698607-1.041483-0.206379H-0.1998813.607697-0.298467H2.1449143.4796040.499562H5.419240-0.1386520.607927C4.186280-2.435929-0.424676H3.528309-3.1029850.143255H4.024770-2.673924-1.481534C5.640468-2.661653-0.039164H5.809227-2.4573671.020222H5.912754-3.701058-0.228565H6.309326-2.027145-0.624800

S14

C3.7861391.3078260.464322O2.400866-0.917023-0.601303O4.3997302.2691790.933159Numberofimaginaryfrequencies=1(-216.2400)ZPEEnergy=-1105.608500FreeEnergy=-1105.673300TS-2+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.8407911.047335-0.997266C-4.6796480.5003170.723409C-3.2449381.305919-1.070588C-2.153920-0.981222-1.202961C-4.515322-0.690879-1.328963C-3.624425-1.7807730.580924H-4.5333371.4546381.226181H-0.0225930.433704-1.364566H-5.474356-1.162215-1.111190H-5.6931330.1384500.898647H-4.405090-0.571615-2.407469H-0.8403722.084283-1.316067H-3.3334521.583190-2.125303H-3.1112762.206557-0.469245H-1.343230-1.502854-0.690487H-2.043956-1.115646-2.283874H-4.550633-2.3369110.725348H-2.783419-2.3300110.999963N-2.0343370.465649-0.903635N-3.750415-0.4978561.378071N-3.434413-1.530755-0.820976N-4.4609140.623506-0.688139H-4.113522-0.7221542.308494C-0.0386261.4905390.819442C2.3142311.2123160.289461C2.182096-0.1628420.644370C1.024112-0.7035281.138826C-0.1222950.1260971.325207O-1.197086-0.3179561.823615C3.6025791.720393-0.210671C1.2149062.0253640.428664H-0.8368892.1594281.125250H1.3018323.0754710.167746O3.241859-1.0070730.508773H-2.771266-0.1397431.516298C4.6355840.713181-0.363693C4.418491-0.568884-0.013336C5.364233-1.703730-0.159232

H0.990702-1.7453511.435587C4.724005-2.845283-0.957589O3.7757162.905066-0.486100H5.5977991.004465-0.763990H5.629165-2.0593700.842824H6.271111-1.347509-0.646892H4.484507-2.519613-1.972608H3.804972-3.187393-0.477072H5.411440-3.689828-1.021153Numberofimaginaryfrequencies=1(-358.0582)ZPEEnergy=-1105.600987FreeEnergy=-1105.669624TS-3+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C0.307503-0.7591100.891276C-2.948685-0.524691-1.587342C-1.712589-1.8168430.068253C-1.8817270.1254481.644663C-3.798761-0.8414850.617403C-3.1956001.357726-0.023582H-2.282383-0.926485-2.351248H0.724215-0.1868611.717770H-4.805770-0.6349300.252675H-3.958911-0.449770-2.001048H-3.855271-1.5418651.452475H0.747105-1.7505700.781583H-1.861055-2.6473760.767913H-1.064520-2.154102-0.743585H-1.3481391.0537381.853134H-2.049455-0.4131162.584340H-4.2400991.564166-0.275296H-2.7130052.2866460.282953N-1.038634-0.7113320.767315N-2.4742280.838459-1.220346N-3.1863370.4067221.071295N-3.006092-1.437682-0.458966H-2.6958801.453815-2.004283C1.140354-0.007199-0.593325C3.4434050.4333150.116593C3.1494161.7558720.434215C1.8645642.2265060.203798C0.8745351.397809-0.353402O-0.3177861.879369-0.552508H1.6061123.2533540.428894C2.503159-0.386124-0.430725H0.564234-0.512051-1.364516

S15

H-1.1136181.227896-0.919931O3.019688-1.604543-0.683252O4.649908-0.2346570.176902H3.9124082.4061120.846871C4.307671-1.601467-0.024724H4.196767-2.1053500.939491H5.040350-2.076310-0.671020Numberofimaginaryfrequencies=1(-415.8955)ZPEEnergy=-950.821928FreeEnergy=-950.882201TS-3+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.009520-1.1672040.704410C-3.338884-0.239860-1.475566C-2.244139-1.7790130.067777C-1.8636360.1476151.641675C-4.021247-0.3979720.803789C-3.0420541.6312230.076395H-2.856404-0.765943-2.299898H0.631313-0.7169231.474695H-4.9936990.0139750.531510H-4.3508840.045686-1.781935H-4.142953-1.0819001.645473H0.239574-2.2046070.481146H-2.496408-2.5736190.778478H-1.750317-2.222884-0.798861H-1.1298860.9409451.785549H-2.050352-0.3484592.600203H-4.0439442.043990-0.079965H-2.3614732.4451360.329090N-1.291241-0.8537560.712420N-2.5495800.978912-1.166156N-3.1273700.6947641.184276N-3.471222-1.132745-0.336818H-2.6883891.635257-1.934902C0.932682-0.506727-0.903369C3.256577-0.634002-0.383644C3.2028140.7034560.093492C2.0810231.4778510.030377C0.9340230.870573-0.529072O-0.1586851.589209-0.591401H2.0560372.5036680.373195C2.179423-1.235504-0.925279H0.158984-0.824183-1.595843H-1.0322871.114786-0.935334H2.218777-2.245602-1.313543

O4.540542-1.086316-0.252641O4.4101711.0517780.558966C5.221681-0.1362860.558959H5.295243-0.5052761.583888H6.1900390.0934620.121937Numberofimaginaryfrequencies=1(-385.5505)ZPEEnergy=-950.828929FreeEnergy=-950.888805TS-4+HMTA+-R2

RM062X/6-311+G(d,p)(AceticAcid)11C0.078405-0.785480-0.749978C3.782494-0.8906361.304227C2.157240-1.897628-0.214631C2.1060200.279949-1.558673C4.133398-0.870767-1.053052C3.7613691.241081-0.024900H3.260224-1.3651852.133025H-0.461009-0.138293-1.435850H5.200391-0.736386-0.874061H4.855287-0.8777611.497625H3.987021-1.442948-1.969994H-0.385113-1.716977-0.442177H2.131027-2.664227-0.993173H1.651261-2.2645560.678979H1.5721311.228045-1.475981H2.069218-0.075401-2.591640H4.8346211.4188340.046074H3.2199342.184198-0.064697N1.385421-0.725172-0.724073N3.3372470.5494681.251060N3.4939340.436939-1.187546N3.537138-1.5924660.072117H3.7428921.0485242.047962C-0.9447010.1421191.022923C-2.8585490.979719-0.262079C-2.1268132.145404-0.591168C-0.8616842.323522-0.099587C-0.2345081.3508210.757539O0.9518821.5328301.197880H-0.2973743.220779-0.329382C-2.2760230.0263010.567405H-0.537050-0.5480541.753731H2.2864850.6737331.325912H-2.5857172.890966-1.232250C-4.559910-0.433168-0.229140N-4.1473040.696350-0.688756

S16

S-3.392222-1.2815960.795758C-5.894832-1.039961-0.494908H-5.788803-1.998322-1.008796H-6.436370-1.2146450.437443H-6.475044-0.362925-1.121411Numberofimaginaryfrequencies=1(-164.6066)ZPEEnergy=-1292.053326FreeEnergy=-1292.109075TS-4+HMTA+-R6

RM062X/6-311+G(d,p)(AceticAcid)11C0.4100301.2894010.544579C4.2290240.391123-1.032824C2.7742771.7538600.377745C1.924973-0.3593311.503667C4.2505690.1579021.337918C3.429794-1.7006640.109731H3.9728251.034179-1.872997H-0.3651380.8196281.143838H5.246978-0.2792061.266971H5.2691240.073368-1.109544H4.1586560.7059802.276088H0.3062012.3513420.351445H2.8638142.4407741.224357H2.5311602.319592-0.522750H1.160218-1.1098291.296784H1.854265-0.0443942.549041H4.409964-2.1766000.144337H2.645911-2.4491570.011670N1.6471340.8275300.654684N3.389354-0.859553-1.147505N3.249549-0.9077941.295630N4.0386861.0746780.218373H3.736860-1.420084-1.930497C-0.4855440.834793-1.307349C-2.7581120.714323-0.531268C-2.534252-0.664922-0.215699C-1.352262-1.310713-0.481329C-0.291840-0.579144-1.100233O0.820120-1.130994-1.383596H-1.206887-2.364583-0.273896C-1.7518761.438314-1.117921H0.2589581.345423-1.909534H2.368431-0.667659-1.345409H-1.9105492.480099-1.375506C-4.7625220.2805510.309374N-4.0312921.190100-0.218202

S-3.987649-1.3131800.499675C-6.1709930.4578270.757178H-6.4750901.4894610.583551H-6.835439-0.2101380.203499H-6.2704440.2259811.820233Numberofimaginaryfrequencies=1(-286.5792)ZPEEnergy=-1292.048428FreeEnergy=-1292.105380TS-5+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.184770-0.314523-1.069636C3.101252-1.2701211.377432C1.600673-1.820882-0.469130C2.0920710.446799-1.512275C3.818052-1.077508-0.888197C3.6299730.9528680.327810H2.381583-1.7208462.058563H-0.5118570.482947-1.731109H4.852454-1.146604-0.550747H4.116622-1.4670771.722469H3.728582-1.525429-1.878544H-0.803520-1.204718-1.009607H1.584331-2.471833-1.347489H0.911031-2.2087940.282001H1.7125211.463288-1.400289H2.1563360.194314-2.574620H4.6933120.9309200.566146H3.2616121.9768380.330143N1.112161-0.481385-0.887359N2.9103390.2264161.442793N3.4205240.328702-0.950013N2.949518-1.7946650.045799H3.2734250.5651022.338468C-1.1715150.4349910.656059C-3.0230521.566046-0.444388C-2.2194972.731593-0.535364C-0.9573092.774016-0.007933C-0.3948501.6343370.663860O0.7714451.6696361.169463H-0.3599133.678533-0.053704C-2.5114260.4552490.177372H-0.849704-0.3861871.288431H1.8978770.5346681.398540C-3.273095-0.8189060.255261H-4.0241751.560186-0.855630O-2.754724-1.8860940.508788

S17

O-4.568948-0.6804910.001804C-5.351265-1.8842180.027735H-2.6248133.609394-1.026992H-5.324548-2.3236771.025302H-6.363258-1.580997-0.227576H-4.969336-2.596367-0.704370Numberofimaginaryfrequencies=1(-253.6348)ZPEEnergy=-990.142428FreeEnergy=-990.199155TS-5+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.4055441.277691-0.991268C-4.1556100.3468020.784381C-2.8258291.311359-1.021065C-1.527318-0.866150-1.210653C-3.907000-0.790202-1.294183C-2.889743-1.8184690.591079H-4.1003681.3031701.301357H0.4668880.773812-1.398909H-4.816936-1.350288-1.075875H-5.124956-0.1193710.962199H-3.820920-0.642479-2.371276H-0.5060562.333912-1.216974H-2.9557591.592712-2.069930H-2.7659912.212967-0.409737H-0.661884-1.314579-0.719155H-1.426126-0.976133-2.294702H-3.759374-2.4584110.741499H-1.994612-2.2905520.990893N-1.5346770.585202-0.896352N-3.121498-0.5627421.405716N-2.746833-1.535682-0.810918N-3.9661410.513310-0.631040H-3.434382-0.8293942.343722C0.4726701.7183440.851885C2.7779481.5848160.109190C2.7375620.1807290.345271C1.635847-0.4289700.885384C0.4669610.3343771.226561O-0.553082-0.2129381.740490H3.6792652.041246-0.277034H1.637070-1.4933071.094885C1.6746242.3350460.404337H-0.3387222.3353351.224899H-2.184372-0.1015371.521060H1.6849073.4073450.240987

C3.915190-0.6875170.026854O3.956065-1.8757820.245996O4.916749-0.015180-0.530531C6.085183-0.784589-0.856182H5.828622-1.568562-1.569160H6.504564-1.2252190.048543H6.785677-0.079691-1.296319Numberofimaginaryfrequencies=1(-332.2469)ZPEEnergy=-990.138117FreeEnergy=-990.195256TS-6+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.5514730.176894-1.040796C-4.1144601.0605931.002933C-2.5912791.451769-0.863376C-2.648661-1.026058-1.405419C-4.6336320.279980-1.187439C-4.215322-1.3933270.444351H-3.5204721.7550811.594510H-0.059157-0.675231-1.501401H-5.6865110.244030-0.906470H-5.1688661.1562651.263130H-4.5491490.519399-2.247959H-0.0906161.148835-1.182578H-2.6163811.890697-1.864880H-2.0254832.104131-0.195830H-2.126522-1.924049-1.072846H-2.677182-1.001447-2.498897H-5.282718-1.5049970.635411H-3.687448-2.3144790.683617N-1.8728820.154881-0.946509N-3.701941-0.3377581.400942N-4.017620-1.021503-0.929821N-3.9534801.311917-0.403604H-4.073589-0.5330382.334772C0.3749410.0173030.827605C2.497318-0.9015430.127720C1.930859-2.2041500.213229C0.658356-2.3979340.662997C-0.167458-1.2860061.047807O-1.348426-1.4491441.473260H0.251049-3.3979750.763489C1.7528780.1945370.482976H-0.1524240.8554711.270498H-2.657122-0.4716141.461342C2.2900181.5876200.484184

S18

Br4.279040-0.799566-0.515607O3.4184591.9007220.761802O1.3404782.4719550.162707C1.7356873.8531090.195645H2.536351-3.056320-0.073127H0.8464264.418209-0.072430H2.0710454.1215811.197771H2.5331224.032507-0.525572Numberofimaginaryfrequencies=1(-329.9057)ZPEEnergy=-3563.716707FreeEnergy=-3563.796897TS-6+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.960668-1.018344-0.922000C4.869241-0.7417270.711254C3.335780-1.464098-1.043014C2.4263370.902443-1.207904C4.7541660.418978-1.365565C3.9901861.6101010.542850H4.666674-1.6734331.236517H0.170290-0.371655-1.294677H5.7533780.813477-1.178680H5.909767-0.4499850.855826H4.6100870.287049-2.438417H0.870563-2.075219-1.149767H3.378359-1.761244-2.094705H3.142325-2.342582-0.425941H1.6662541.496389-0.697751H2.3124491.018484-2.290008H4.9622232.0892550.660711H3.2052972.2320150.968362N2.193288-0.526988-0.875379N4.0293670.3348911.360230N3.7550761.355044-0.852420N4.607088-0.873435-0.695370H4.4198540.5463732.283018C0.110555-1.3123020.958327C-2.176043-0.8511460.339006C-1.9392160.5377620.560751C-0.7423900.9734791.057686C0.3301910.0540801.333026O1.4392120.4505491.789505H-0.5877412.0265271.269549C-1.188474-1.7578570.588279H0.833488-2.0445371.303255H3.0341750.0425141.514687

H-1.367689-2.8189210.458307C-2.9866701.5758390.287325O-3.4244042.3167021.132338O-3.3385411.604578-0.988826C-4.3832052.531202-1.335159H-4.0660753.551161-1.117777H-5.2880272.292639-0.774970H-4.5478212.398431-2.401074Br-3.907098-1.457384-0.163977Numberofimaginaryfrequencies=1(-344.4168)ZPEEnergy=-3563.713384FreeEnergy=-3563.793547TS-7+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.0466440.6544010.948308C3.6504170.900656-1.074861C2.1493911.6359410.703989C1.855149-0.7864181.423463C4.0029110.2270621.185201C3.405248-1.490463-0.339091H3.1749011.624606-1.734351H-0.643851-0.0759561.487322H5.0482990.0296600.946128H4.7143580.829962-1.302710H3.9232320.5572822.221497H-0.3842911.6858020.965797H2.2081852.1493321.667807H1.6955982.298228-0.034372H1.224582-1.6248301.123248H1.851859-0.6992612.513729H4.454421-1.747971-0.484956H2.770312-2.353443-0.529608N1.2571160.4582870.871612N3.054466-0.451994-1.382535N3.223550-0.9966520.999514N3.4891111.2760600.304299H3.404872-0.770226-2.290555C-1.0731840.387220-0.902248C-3.198217-0.3728440.024562C-2.672963-1.6919740.022965C-1.423058-1.976344-0.463828C-0.583031-0.952639-1.003976O0.575780-1.201474-1.472975H-1.059722-2.997805-0.477582C-2.4011630.629165-0.476805H-0.5423901.169471-1.434195

S19

H1.998555-0.445204-1.454477H-3.279951-2.5014010.409778Cl-2.9776752.270897-0.483055O-4.437526-0.0504440.478795C-5.278861-1.1054580.930930H-4.847064-1.6101091.799371H-6.214348-0.6302731.219273H-5.468786-1.8275060.132344Numberofimaginaryfrequencies=1(-248.2234)ZPEEnergy=-1336.408275FreeEnergy=-1336.473527TS-7+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.1377711.105661-0.788377C-3.8860030.6689221.096613C-2.4622111.732192-0.579116C-1.784403-0.572497-1.423053C-4.0660370.097088-1.211026C-3.263965-1.6073800.233786H-3.5441651.4114251.815469H0.5899110.505196-1.327130H-5.076862-0.267194-1.026375H-4.9341770.4297161.278111H-4.0037280.499027-2.222945H0.0458262.171319-0.716324H-2.5718822.289291-1.513503H-2.1335242.4078300.211446H-1.044731-1.324238-1.142856H-1.760618-0.419969-2.505760H-4.266299-2.0268470.322332H-2.514292-2.3789650.396398N-1.3960160.713690-0.781948N-3.103647-0.5971591.347770N-3.117583-1.006540-1.064349N-3.7429961.153290-0.251445H-3.430987-1.0180002.222059C0.8930730.8859601.118007C3.1063750.4935370.203676C2.749305-0.8840600.082446C1.546833-1.3717960.505150C0.572509-0.4999191.096412O-0.551240-0.9505771.500498H1.318428-2.4281180.424726C2.1860951.3477890.755313H0.2336251.5484371.668816H-2.060990-0.4383091.462402

H2.4135272.3993790.876417Cl3.909870-1.971900-0.624261O4.3466120.834783-0.225770C4.7088232.205121-0.127241H4.6997602.5381750.914263H5.7196002.275252-0.523997H4.0367692.828591-0.724670Numberofimaginaryfrequencies=1(-221.9056)ZPEEnergy=-1336.408197FreeEnergy=-1336.472324TS-8+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.177531-0.361328-1.069881C3.203210-1.2772671.274997C1.745976-1.753310-0.622372C2.0104490.653860-1.400654C3.879834-0.756935-0.950968C3.5130401.0914090.490919H2.535065-1.8704351.896901H-0.5804320.444759-1.677260H4.918409-0.765999-0.619640H4.234949-1.4165171.598895H3.826436-1.094496-1.986482H-0.716565-1.301825-1.055776H1.782786-2.298264-1.569579H1.105703-2.2873930.080941H1.5366151.611130-1.177184H2.0891800.528668-2.484539H4.5768491.1391290.723951H3.0512912.0687230.614961N1.126425-0.427170-0.888563N2.8724180.1768101.511803N3.3491290.601306-0.851436N3.090544-1.656500-0.108251H3.2046620.4407482.443631C-1.2987150.2751340.679439C-2.9810601.412530-0.600967C-2.1493222.553829-0.639107C-0.9405092.5948150.011672C-0.4867351.4554010.740649O0.6363181.4479911.352493H-3.9402691.448953-1.104115H-0.3229333.4867660.007620C-2.5943180.2839070.095305H-0.992119-0.5436901.320960H1.8343000.3980741.490037

S20

C-3.522030-0.9322740.168930C-3.825207-1.433469-1.252726C-2.916672-2.0850970.974404C-4.837285-0.5128030.844636H-2.910996-1.737222-1.771763H-4.315974-0.663702-1.852551H-4.490956-2.300432-1.207864H-1.983959-2.4512970.534345H-3.621934-2.9200310.991250H-2.719212-1.7978422.010959H-5.3462360.2720710.280610H-4.654793-0.1407361.856826H-5.511171-1.3721850.911975H-2.4875973.427599-1.187575Numberofimaginaryfrequencies=1(-211.4309)ZPEEnergy=-919.430642FreeEnergy=-919.493553TS-8+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.4791061.2849720.816903C3.8090880.223917-1.336597C2.8452871.6028240.424962C2.046649-0.4837161.565239C4.326020-0.1645450.958823C3.105562-1.832051-0.196893H3.4744710.967846-2.060087H-0.2491660.8234151.480270H5.241483-0.6763920.659476H4.783500-0.163278-1.651585H4.4833540.3196121.924234H0.4588102.3716250.833403H3.1567462.1934871.294153H2.5030412.282683-0.358210H1.192233-1.1601511.520910H2.234149-0.2094372.609540H4.040270-2.369924-0.383424H2.287719-2.551756-0.144013N1.7146250.7414900.810018N2.822295-0.890159-1.315744N3.244814-1.1432811.073802N3.9903480.851471-0.039869H2.932972-1.408071-2.188055C-0.3674761.110387-0.872967C-2.7289981.491760-0.412247C-2.9275330.084758-0.201589C-1.877775-0.778640-0.415683

C-0.608756-0.295552-0.809286O0.348323-1.157780-0.992535H-3.5619612.173002-0.291685H-1.979361-1.850050-0.299713C-1.5155951.974215-0.780847H0.4753671.444137-1.472457H1.335683-0.793762-1.196893H-1.3722033.036851-0.945536C-4.302730-0.3960790.241625C-5.330444-0.017146-0.838947C-4.351380-1.9095020.457477C-4.6673580.3011391.563789H-6.322342-0.359687-0.531366H-5.3823991.062464-0.995659H-5.086551-0.491700-1.793507H-5.353774-2.1913550.788664H-4.139870-2.459597-0.463445H-3.643672-2.2319521.226203H-5.650051-0.0428181.897940H-3.9403380.0630142.345540H-4.7112561.3869401.455554Numberofimaginaryfrequencies=1(-405.0519)ZPEEnergy=-919.429126FreeEnergy=-919.491586ProductsP-1+HMTA+-R2

RM062X/6-311+G(d,p)(AceticAcid)11C-1.6818000.325708-0.440207C-3.0644950.862470-0.212360C-4.0152210.0595180.297848C-3.756844-1.3487120.531594C-2.600211-1.9506340.178487C-1.558389-1.177113-0.476150O-0.567277-1.713086-0.974531C-0.7779100.7728090.768684N0.6170370.5023320.502756C1.352879-0.0926031.621043N2.704725-0.4615991.208698C3.3924330.7287780.702982N2.6883261.268116-0.463464C1.3339611.645367-0.067119C2.7252420.311538-1.535785N2.190650-1.050116-1.126354C2.738983-1.5020070.217646H1.157035-1.022705-1.069555

S21

H-1.2377890.751190-1.345185H-5.0043330.4467480.515900H-4.549017-1.9407780.979668H-2.439299-3.0153040.302228H-1.1019000.2287671.660774H-0.9540331.8380870.957323H0.817798-0.9849531.953023H1.4476920.6044552.466379H4.4140500.4681340.422888H3.4131391.4856121.487413H1.4196622.4659970.660370H0.7867032.006676-0.941344H3.7570460.151541-1.849122H2.1253470.645745-2.380982H2.452321-1.736929-1.838997H2.142879-2.3596200.526588H3.770659-1.8053890.038684C-3.2960712.303339-0.537130H-4.2939182.623870-0.236167H-2.5590162.947613-0.047400H-3.1873162.464054-1.614896Numberofimaginaryfrequencies=0ZPEEnergy=-801.622003FreeEnergy=-801.682022P-1+HMTA+-R4

RM062X/6-311+G(d,p)(AceticAcid)11C0.580965-1.8108280.962927C-2.0306870.230743-1.737360C-1.488957-1.677600-0.339080C-1.219409-0.2792811.604491C-3.197770-0.1337490.292260C-1.6960711.7045100.291901H-1.452863-0.209897-2.548759H0.459456-2.0925782.016171H-3.9788210.530951-0.079501H-2.8591810.816407-2.135523H-3.645155-0.9007640.924161H0.588225-2.7389290.386709H-1.994877-2.4748510.223898H-0.957567-2.122264-1.182577H-0.5004460.2802692.202329H-1.730845-1.0041742.253891H-2.4882462.4048170.027185H-0.8901152.2227950.811813N-0.514766-0.9634860.506947N-1.1117911.212553-1.026640N-2.2338990.6331501.083903

N-2.524256-0.775097-0.839550H-0.2432860.707494-0.813567C1.970418-1.1184810.791654C2.0525191.3230211.270754C1.9967451.605397-0.170189C2.2127610.478324-1.084895C2.208232-0.795273-0.655120H2.0527912.1744041.943198C2.0487720.0593271.705033H2.707136-1.8653221.113519H2.044917-0.1540352.771094O1.7471332.733505-0.593859H-0.8944042.012526-1.628859H2.3454990.724320-2.134637C2.379471-1.947637-1.595164H1.437329-2.493463-1.711802H2.701317-1.608524-2.580090H3.113128-2.657896-1.203672Numberofimaginaryfrequencies=0ZPEEnergy=-801.620777FreeEnergy=-801.680723P-1+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C1.395098-0.801558-0.661542C2.653416-1.600255-0.582009C3.809317-1.066099-0.175876C3.9093160.3548270.162348C2.8446841.1775410.007128C1.5873380.689552-0.527034O0.6745111.465414-0.823196C0.455474-1.2613090.504264N-0.872828-0.7039140.368854C-1.475875-0.2420841.620544N-2.7433750.4368931.360387C-3.641073-0.4815700.655565N-3.059259-0.882896-0.627451C-1.790572-1.564109-0.379681C-2.9321270.265258-1.483586N-2.1547131.396010-0.832236C-2.5989301.6492240.600500H-1.1425511.170827-0.831783H0.866854-1.003353-1.599341H2.581811-2.658157-0.816095H4.704743-1.672300-0.087098H2.9139492.2393730.219036H0.897295-0.9368331.451029H0.438732-2.3591590.514340

S22

H-0.7849450.4507322.105279H-1.686737-1.0751752.307524H-4.6009490.0076170.483005H-3.793327-1.3698321.268710H-2.015398-2.4876040.174436H-1.330717-1.831753-1.333868H-2.4082470.010499-2.403816H-3.9201130.665712-1.712051H-2.2903642.251754-1.377222H-1.8536912.3066351.046763H-3.5605912.1585310.535771C5.2291500.8492340.659543H5.5258550.2892081.551680H6.0013950.673108-0.096051H5.2008391.9122930.897456Numberofimaginaryfrequencies=0ZPEEnergy=-801.623131FreeEnergy=-801.683037P-1+HMTA+-R2(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11C-0.6992030.5809530.637542C-1.9175810.218243-0.226456C-4.616436-0.6911160.024778C-3.0566001.1856800.001583C-2.267573-1.261394-0.120393C-3.665010-1.640532-0.088665C-4.3151210.7259440.085892O-1.364961-2.098372-0.090420N0.518094-0.2158560.296447C1.5912060.0163221.317429C0.986479-0.000443-1.152256N2.396157-0.214632-1.292975N2.822130-0.7207531.001826C2.785335-1.270503-0.355456C4.0116980.1603141.074147C3.2175211.024638-1.048706N4.3600090.779921-0.203246H5.0367370.209771-0.698243H0.219740-1.2022080.355429H-0.9219380.3935991.690198H-0.4292211.6285780.508851H-1.6496960.353520-1.288803H-5.658843-0.9883800.083573H-3.896381-2.699098-0.102680H-5.1394331.4215040.194473H1.7523851.0962981.363435H1.169887-0.3144742.267742

H0.415217-0.725901-1.733969H0.7079661.013265-1.441629H2.082006-2.100614-0.437055H3.771268-1.664669-0.591033H4.866679-0.4290871.404900H3.8196240.9261571.828474H3.5649691.404585-2.008315H2.5918371.796508-0.587782C-2.7380492.6486770.040980H-2.2194152.9179760.966862H-2.0857032.929542-0.791976H-3.6527293.238648-0.015970Numberofimaginaryfrequencies=0ZPEEnergy=-801.587941FreeEnergy=-801.649428P-1+HMTA+-R4(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11C0.576929-1.7740630.938925C-1.7731630.875978-1.558780C-0.961350-1.336285-0.886554C-1.600411-0.8367881.424803C-3.155605-0.634922-0.347756C-2.4253241.3588980.718072H-2.6470561.321333-2.041746H0.427856-2.0242841.991805H-4.028655-0.086602-0.706543H-0.9262070.950318-2.243543H-3.428623-1.682587-0.202224H0.657047-2.7165070.386281H-1.275813-2.391799-0.878976H-0.134782-1.230391-1.594734H-1.210166-0.3741562.335834H-1.976264-1.8401671.677405H-3.3735191.8474970.478492H-2.0464231.7822941.649523N-0.486180-0.9397650.454476N-1.4700901.649478-0.352619N-2.723608-0.0646780.928299N-2.089017-0.545659-1.345642H-0.5624321.340861-0.022190C2.023591-1.0793740.860397C1.8915271.3390691.333959C1.9716041.562875-0.076702C2.2247160.517974-0.998313C2.320641-0.763906-0.554745H1.7783372.1894191.997240C1.9658690.0696991.778343

S23

H2.698477-1.8549631.237236H2.3634590.781438-2.040692H1.897637-0.1433622.840784O1.8412912.757446-0.583840H1.6633863.4377190.085815C2.678309-1.884704-1.467233H2.691088-1.566567-2.509055H3.672842-2.256283-1.197455H1.987757-2.725124-1.350625Numberofimaginaryfrequencies=0ZPEEnergy=-801.592647FreeEnergy=-801.652148P-1+HMTA+-R6(noH-Bond)RM062X/6-311+G(d,p)(AceticAcid)11C-0.4208610.8177800.637890C-1.6503120.589218-0.250147C-4.453352-0.0658870.014824C-2.6914521.6278410.033344C-2.147893-0.845763-0.186221C-3.574476-1.082650-0.149791C-3.9858331.3172420.133541O-1.331838-1.769357-0.189231N0.728415-0.0634310.270145C1.7949240.0064441.324338C1.2383470.186127-1.158538N2.626042-0.142436-1.292084N2.975949-0.7962430.979650C2.913098-1.272129-0.404107C4.226373-0.0055591.107535C3.5389801.011391-0.975318N4.6481090.631903-0.137456H5.2745040.022739-0.652401H0.337162-1.0192920.268197H-0.6689360.6033611.679373H-0.0785811.8506040.556779H-1.3607420.735015-1.304235H-2.3544232.6569700.111293H-3.902660-2.115391-0.197829H-4.7284872.0895670.303345H2.0375351.0640261.453359H1.323886-0.3581872.238219H0.615261-0.453767-1.785498H1.0556861.234180-1.397341H2.144909-2.035451-0.534541H3.865778-1.735295-0.651030H5.030232-0.6639481.435883H4.0708350.7474691.882914

H3.9219441.415684-1.911302H2.9725331.803608-0.473548C-5.925943-0.2980180.101888H-6.3113460.1007071.045263H-6.4345180.243753-0.701871H-6.175061-1.3562700.031618Numberofimaginaryfrequencies=0ZPEEnergy=-801.590561FreeEnergy=-801.652086P-2+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.411749-0.453141-0.522912C-1.879621-0.309948-0.338722C-2.683219-1.3209610.069251C-2.106326-2.6408550.255074C-0.818067-2.920173-0.017852C0.066381-1.888758-0.548238O1.195010-2.148578-0.952164C0.2955430.2475150.692157N1.7169720.3539240.468361C2.1038691.600239-0.200929N3.5269641.599251-0.527343C4.2982581.3983540.701557N3.9567550.1116661.312656C2.5383470.1088051.658765C4.335042-0.9608220.432936N3.743366-0.811013-0.959899C3.8919340.602887-1.496006H4.214171-1.461551-1.594776O-2.3188170.937504-0.548249C-3.6338091.241261-0.343304C-4.5134470.3067940.062828C-4.107700-1.0670510.299786O-4.883562-1.9481880.666161C-3.9130692.681811-0.601718C-3.1614713.5913800.374680H-0.0981480.057160-1.438054H-2.777070-3.4162710.611497H-0.411029-3.9187740.087876H0.101950-0.3449771.591026H-0.1756301.2280560.837281H1.5205131.709430-1.118162H1.9100442.4704730.443016H4.0636122.1983021.403583H5.3637461.4203960.469294H2.3848840.8802052.427077H2.266047-0.8638692.073343

S24

H3.994418-1.9218470.815686H5.417325-0.9671040.303536H2.741459-1.064059-0.924751H4.9421580.718582-1.763978H3.2684370.670103-2.386164H-5.5496120.5806070.215971H-3.6158802.909076-1.630464H-4.9897022.836746-0.522697H-2.0810863.4655740.279137H-3.3997914.6359850.168062H-3.4456293.3710341.406134Numberofimaginaryfrequencies=0ZPEEnergy=-1105.625973FreeEnergy=-1105.691938P-2+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C1.246986-1.076175-0.887353C2.330994-0.354935-0.517144C2.3028721.085933-0.309443C1.1349071.737158-0.435126C-0.1447621.030629-0.679778C-0.012371-0.409384-1.114112O-0.979783-1.004942-1.594389C-0.9245811.0332180.691973N-2.2522750.4862470.549429C-3.2939151.5050560.393077N-4.5911620.8913680.122978C-4.913117-0.0396491.208289N-3.906824-1.0991501.284210C-2.606612-0.5039651.571037C-3.932826-1.8830290.080682N-3.778604-1.034512-1.172546C-4.6548260.204287-1.137570H-4.029818-1.599754-1.988121O3.497010-1.026750-0.356349C4.649955-0.383788-0.004795C4.7229380.9452370.193339C3.5604611.7972030.043363O3.5861243.0090440.201438C5.776203-1.3489390.129832C5.504858-2.3994241.210926H1.328581-2.138941-1.080072H1.1079542.811254-0.274033H-0.7657811.575793-1.396538H-0.9459412.0652101.061147H-0.3470420.4425461.408890H-3.0213962.162383-0.436112

H-3.3990732.1120501.304265H-5.894698-0.4814051.030064H-4.9286340.5067982.151164H-2.665566-0.0536902.572840H-1.842478-1.2846251.577047H-4.895383-2.386733-0.008978H-3.121984-2.6103440.067057H-2.783076-0.764184-1.265652H-4.3282850.847270-1.953629H-5.674306-0.138838-1.315256H5.6687711.3923660.469064H5.914543-1.839450-0.839384H6.682548-0.7861360.354988H4.622760-2.9953320.970787H6.358924-3.0738131.290039H5.351646-1.9255032.183151Numberofimaginaryfrequencies=0ZPEEnergy=-1105.614098FreeEnergy=-1105.679395P-3+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C1.181295-0.100998-0.541457C2.601175-0.434086-0.331871C3.5022870.4156460.167836C3.1877841.7735060.474079C1.9437082.2421220.200786C0.9374231.398139-0.432984O-0.1281731.864220-0.835045C0.346882-0.7883520.601089N-1.068981-0.5798490.417263C-1.770015-0.0486941.589451N-3.1541720.2772651.259145C-3.818867-0.9216180.744736N-3.155523-1.386178-0.476152C-1.770352-1.726864-0.164188C-3.288115-0.396113-1.509179N-2.7923030.971711-1.074521C-3.2882101.3498760.312588H-1.7579520.994208-1.058540O3.121090-1.689934-0.425065C4.538710-1.478245-0.273244O4.684778-0.2537630.440313H0.803307-0.464742-1.500561H3.9464942.4130980.912331H1.6781073.2766320.380017H0.676195-0.3759251.559528

S25

H0.607391-1.8529790.599577H-1.793193-0.7765852.413606H-1.2536800.8532301.925315H-4.863800-0.6947510.527765H-3.765977-1.7083331.497385H-1.254039-2.029047-1.078325H-1.788529-2.5795460.530079H-4.340843-0.270653-1.763266H-2.719063-0.674028-2.394971H-3.1151221.675189-1.744234H-2.7126152.2219060.620811H-4.3407111.6112270.200930H4.970471-2.2963550.295991H4.976622-1.373278-1.271055Numberofimaginaryfrequencies=0ZPEEnergy=-950.841995FreeEnergy=-950.903377P-3+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.937289-0.582706-0.742574C2.250268-1.309285-0.738911C3.323351-0.663041-0.300697C3.2883530.7309600.111373C2.1979591.5185610.025425C1.0048250.924901-0.540127O0.0187581.616702-0.807834C0.055750-1.1620810.412086N-1.313622-0.7009910.332104C-1.895255-0.2796301.607031N-3.2152780.3117421.400385C-4.074891-0.6648360.728373N-3.519669-1.020517-0.579476C-2.199433-1.615929-0.388435C-3.5100220.136418-1.431280N-2.7899901.319240-0.806211C-3.1889171.5346000.644737H-3.0101332.163460-1.341469O4.613650-1.093903-0.180661C5.322647-0.1079930.553980O4.5073871.0752240.531823H0.404723-0.764742-1.681321H2.283108-2.350813-1.036218H2.2096542.5684760.287758H0.495368-0.8555121.366401H0.117753-2.2573330.368848H-2.020714-1.1237632.301474H-1.2338540.4587632.064980

H-4.140136-1.5626231.342979H-5.072723-0.2428850.597750H-2.338949-2.5583250.162441H-1.759191-1.842672-1.362449H-3.009827-0.075737-2.375214H-4.5335390.464046-1.614662H-1.7646051.174105-0.846792H-2.4735272.2407981.064179H-4.1861521.9746690.625249H5.442824-0.4255261.590832H6.2699370.1054810.065111Numberofimaginaryfrequencies=0ZPEEnergy=-950.857321FreeEnergy=-950.918637P-4+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C0.7238440.199954-0.490446C2.186877-0.002061-0.298490C3.0242580.9685280.169453C2.5304592.3059080.415638C1.2527712.6367860.141479C0.3306101.667502-0.446492O-0.7754052.014677-0.851609C-0.047975-0.5083670.677086N-1.473761-0.4952400.452265C-2.279435-0.2198801.644697N-3.691511-0.0948751.293716C-4.133376-1.3284400.639140N-3.373348-1.550737-0.592722C-1.958090-1.681176-0.260117C-3.652656-0.499287-1.529794N-3.4024850.883416-0.949174C-3.9774081.0336140.450541H-2.3851781.069984-0.916289H0.370500-0.224995-1.433767H3.2254193.0391760.812483H0.8777093.6434890.283193H0.1904230.0100141.610829H0.342878-1.5305710.767624H-2.195930-1.0245472.389780H-1.9314060.7138712.091190H-5.196266-1.2554410.404089H-3.969873-2.1667341.316058H-1.379033-1.807691-1.177815H-1.845842-2.5875440.353317H-4.706009-0.527031-1.808771H-3.027939-0.585575-2.417625

S26

H-3.8316471.583147-1.560794H-3.5582851.9494470.864905H-5.0555731.1355440.325370C4.519532-0.6486360.068858S3.068367-1.466860-0.494008N4.3377770.5957170.369680C5.811863-1.3831180.179150H6.602473-0.6725080.418325H5.759986-2.1354600.969979H6.058636-1.890177-0.755649Numberofimaginaryfrequencies=0ZPEEnergy=-1292.073704FreeEnergy=-1292.129188P-4+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.366635-0.617830-0.814488C1.678496-1.322898-0.796359C2.790524-0.690643-0.400241C2.7487020.735499-0.052216C1.6335471.496259-0.155281C0.4219380.887284-0.665826O-0.5696741.572146-0.931501C-0.479776-1.1708380.389864N-1.847278-0.7077610.339687C-2.390834-0.2713991.627484N-3.7194540.3090971.455150C-4.595619-0.6800770.825150N-4.082624-1.047556-0.496199C-2.753527-1.632978-0.343903C-4.1123000.098700-1.361064N-3.3802641.294808-0.775724C-3.7265411.5233780.686826H-3.6285802.130635-1.311779H-0.188162-0.855920-1.727585H1.703360-2.379979-1.040844H1.6209532.5580410.059732H-0.008337-0.8398161.319904H-0.418218-2.2662060.367108H-2.487808-1.1068892.336367H-1.7186800.4764112.053327H-4.636382-1.5707771.452094H-5.599482-0.2646120.723301H-2.868144-2.5708200.219992H-2.344816-1.866463-1.329908H-3.643977-0.119951-2.319769H-5.1442240.416026-1.512265H-2.3565721.157386-0.857280

H-3.0003712.2371981.073451H-4.7260821.9584700.699207N4.057977-1.274344-0.270687S4.3373651.2319490.450352C4.928738-0.4440780.145844C6.362614-0.7392850.396578H6.560694-1.7871870.175378H6.994756-0.108133-0.233373H6.615530-0.5320471.439520Numberofimaginaryfrequencies=0ZPEEnergy=-1292.063305FreeEnergy=-1292.118534P-5+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C1.0131250.494168-0.318448C2.4853940.407115-0.072518C3.2068421.4770840.293950C2.5823812.7887020.393097C1.3005322.9982710.041262C0.4888821.896845-0.479891O-0.6151962.101962-0.974771C0.246997-0.1129510.914096N-1.143895-0.3238160.588632C-2.0923040.0116521.651756N-3.464829-0.0883281.159912C-3.697616-1.4463400.661792N-2.788205-1.748496-0.445472C-1.411126-1.6518860.030797C-3.072256-0.882471-1.556028N-3.0400060.588456-1.172480C-3.7767390.8642160.130095H-3.4706431.137824-1.921178C3.082506-0.948044-0.209480O2.435835-1.919108-0.538801O4.382136-0.9891730.058911C5.012693-2.274542-0.055796H0.732926-0.097834-1.193457H4.2647021.3879890.508417H3.1926333.6170710.736310H0.8469713.9824720.069439H0.3334390.5799191.756332H0.747593-1.0446691.203857H-2.002001-0.6667252.512633H-1.8974001.0336151.983633H-4.729687-1.5369170.319953H-3.522084-2.1556731.470368H-1.266111-2.4374190.786674

S27

H-0.722762-1.836347-0.797232H-2.343768-1.016404-2.354398H-4.078019-1.077822-1.928143H-2.0592010.899991-1.067844H-4.8399120.815386-0.105368H-3.5040421.8741430.433788H6.061634-2.1033650.171430H4.900588-2.658727-1.069790H4.575632-2.9715780.659616Numberofimaginaryfrequencies=0ZPEEnergy=-990.159276FreeEnergy=-990.216287P-5+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.3394831.342826-0.631117C-1.4918702.262461-0.394923C-2.7275311.809526-0.160317C-2.9999320.376902-0.188596C-2.062814-0.530474-0.529373C-0.722180-0.084150-0.918022O0.078995-0.870123-1.412839C0.5328321.3283310.673130N1.7678270.5994580.484132C2.216647-0.1305871.673600N3.404967-0.9231011.370444C4.463647-0.0325380.891093N4.0399090.643323-0.336076C2.8457541.435552-0.056726C3.857573-0.322468-1.382409N2.894889-1.432775-0.988095C3.176048-1.9668070.410417H2.976001-2.199501-1.661329C-4.392806-0.0495790.172883O-5.2547840.7333820.491936O-4.571354-1.3608860.110504C-5.883790-1.8353330.455241H0.2942591.706193-1.445411H-1.2758913.325407-0.358152H-3.5489302.4804570.057737H-2.272065-1.592188-0.581209H-0.0496250.8582501.471025H0.7102772.3713390.968218H2.4772660.5496712.497808H1.411139-0.7902462.002253H5.366809-0.6119120.693875H4.6733330.7147481.656242H3.1298232.2233130.656647

H2.5033921.908445-0.979638H3.4535490.141168-2.281054H4.807410-0.808700-1.605245H1.928411-1.070481-1.028774H4.068902-2.5859430.321747H2.319821-2.5784630.690544H-5.841071-2.9152930.341895H-6.623588-1.408143-0.221912H-6.117801-1.5674151.485788Numberofimaginaryfrequencies=0ZPEEnergy=-990.153455FreeEnergy=-990.212284P-6+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C-0.5322361.4496801.356316C-1.2099030.3162070.631837C-1.9495250.531686-0.459774C-2.1401421.872867-1.008930C-1.5299362.942316-0.477811C-0.6191602.8024660.665908O0.0394763.7412751.072902C0.9100821.0653411.746551N1.6176430.4144370.650196C2.800114-0.3016891.155356N3.530991-0.9605500.079679C3.9258630.040980-0.911765N2.7380890.676082-1.481299C1.9930311.349485-0.422521C1.966019-0.292192-2.206962N1.611550-1.502775-1.358491C2.802699-2.018035-0.561010H0.866513-1.259811-0.692202Br-2.872635-0.866335-1.355069C-1.001552-1.0436791.221643O-0.471556-1.9639430.641924O-1.423882-1.0994042.471372C-1.196716-2.3438373.162080H-1.0815881.6025052.298724H-2.7901831.983330-1.869648H-1.6499093.934218-0.898400H1.4293661.9639012.107222H0.8623380.3563582.577715H3.4991560.3852041.654737H2.464065-1.0498771.877179H4.501095-0.436878-1.705985H4.5390070.800697-0.427243H2.6188892.166638-0.034254

S28

H1.0891321.778487-0.861140H1.0269760.133951-2.558343H2.545925-0.672168-3.048158H1.260714-2.252572-1.961285H2.406755-2.7253180.166641H3.447082-2.529474-1.276262H-1.718702-3.1513012.649204H-0.126714-2.5504353.202794H-1.599734-2.1990674.160437Numberofimaginaryfrequencies=0ZPEEnergy=-3563.734904FreeEnergy=-3563.812736P-6+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C-0.273626-0.833417-0.594567C1.053128-1.487624-0.389020C2.172589-0.770893-0.275669C2.1521050.687928-0.406515C1.0340701.341024-0.768818C-0.2102810.609603-1.018044O-1.1840681.178466-1.494522C-1.073072-0.8813580.756287N-2.446865-0.4756440.564412C-2.9863880.3685131.634807N-4.3286240.8315581.296292C-5.193579-0.3275591.064894N-4.687150-1.122181-0.055925C-3.344245-1.5961410.264607C-4.752053-0.348723-1.265128N-4.0354270.986571-1.143912C-4.3683091.7034580.155412H-3.0144220.834688-1.189176C3.3841561.508988-0.148461O3.8857262.227105-0.975245O3.8095281.3700291.094477C5.0006052.1032941.438036Br3.854523-1.631285-0.064542H-0.852318-1.394060-1.334819H1.065844-2.568847-0.304214H1.0274922.416352-0.910492H-0.583513-0.2131561.470889H-0.994223-1.9001921.156551H-2.3268801.2291831.763338H-3.056277-0.1747362.588501H-6.2062140.0112520.841298H-5.208904-0.9447921.962933H-2.945203-2.154863-0.585068

H-3.428556-2.2773031.124017H-5.791474-0.116213-1.496546H-4.291271-0.879453-2.096763H-4.3042561.581109-1.932640H-3.6486742.5145930.258548H-5.3747982.1038660.033578H5.2067431.8536062.475149H4.8207983.1727171.328221H5.8241671.7917270.794961Numberofimaginaryfrequencies=0ZPEEnergy=-3563.728129FreeEnergy=-3563.808481P-7+HMTA+-R2

RM062X/6-311+G(d,p)(AceticAcid)11C-0.8958520.146954-0.451046C-2.3067540.591467-0.266092C-3.299878-0.2394700.096874C-3.002483-1.6597210.245025C-1.799778-2.190395-0.044989C-0.723463-1.349193-0.552378O0.318509-1.830132-0.987497C-0.0395380.5967550.787841N1.3691800.4074610.536841C2.120678-0.1870151.644651N3.493190-0.4761291.237253C4.1267680.7619800.780136N3.4103151.302815-0.377863C2.0347201.6013410.010662C3.5130080.387202-1.479753N3.043400-1.014357-1.123998C3.592439-1.4819270.215460H2.010044-1.043519-1.083880H-0.4606060.613699-1.339424H-3.796779-2.3121970.588828H-1.615001-3.2551220.032878H-0.3527100.0090631.655775H-0.2796711.6453241.001773H1.625977-1.1139521.942321H2.1715290.4860922.512788H5.1635820.5617630.505736H4.0994141.4925931.588608H2.0709152.4019200.764172H1.4796471.963212-0.858511H4.5567410.290954-1.779580H2.9098420.717192-2.324266H3.351181-1.662911-1.853688H3.033104-2.3759310.487899

S29

H4.640007-1.7292850.043393Cl-2.6044862.290742-0.445968O-4.5376710.2542290.338942C-5.646663-0.6463030.339940H-5.644843-1.2744921.233322H-6.533331-0.0156500.350319H-5.651288-1.262701-0.562179Numberofimaginaryfrequencies=0ZPEEnergy=-1336.424936FreeEnergy=-1336.490070P-7+HMTA+-R6

RM062X/6-311+G(d,p)(AceticAcid)11C-0.6726780.606504-0.600848C-2.0074221.264122-0.471694C-3.1157510.575913-0.163024C-3.028448-0.8826740.008737C-1.904061-1.582530-0.219230C-0.703051-0.895627-0.680451O0.274008-1.534333-1.062074C0.1969750.9691640.652553N1.5785800.5849840.464118C2.2319120.0217881.648145N3.572779-0.4568081.316159C4.3552270.6535320.765903N3.7305011.160977-0.457077C2.3906251.645320-0.137438C3.7458370.144568-1.471882N3.109245-1.153868-1.004207C3.576783-1.5542010.386732H2.079191-1.054526-0.994630H-0.1456110.986066-1.481349H-2.0324482.340599-0.587980H-1.871037-2.660639-0.119812H-0.2186260.4526151.523032H0.0910882.0465520.834679H1.628356-0.8110092.015357H2.3384860.7658382.450951H5.3665400.3106370.542688H4.3997641.4574241.500851H2.5037612.4978490.548546H1.9033081.993639-1.050803H3.1978070.463709-2.357276H4.775796-0.098291-1.733772H3.351779-1.901774-1.659852H2.916193-2.3532690.720497H4.592770-1.9308680.268285Cl-4.461692-1.7068140.514201

O-4.3554101.0783320.013057C-4.5046852.485058-0.134291H-5.5573772.6918880.045272H-3.8926033.0164940.599892H-4.2324822.798285-1.146097Numberofimaginaryfrequencies=0ZPEEnergy=-1336.428003FreeEnergy=-1336.492920P-8+HMTA+-R2RM062X/6-311+G(d,p)(AceticAcid)11C1.1031490.353673-0.345847C2.5655070.221081-0.021823C3.2174901.3031350.447513C2.5797762.6015570.530463C1.3371632.8421480.059427C0.5940911.759216-0.557589O-0.4615821.954946-1.162867C0.275445-0.1721860.889329N-1.129580-0.2826140.566206C-2.0359440.2023411.609138N-3.4197910.1693381.143497C-3.760170-1.2005180.753896N-2.900243-1.647650-0.344973C-1.508100-1.6177530.097409C-3.146133-0.842072-1.509858N-2.9872520.642579-1.233613C-3.6832811.0649310.050945H-1.9819860.879246-1.156689C3.269583-1.133563-0.155993C3.632274-1.6661871.241802C2.414079-2.180247-0.880343C4.565524-0.948285-0.964127H0.816128-0.252534-1.207204H4.2550711.2379790.754436H3.1545183.4187330.955739H0.8946213.8313750.061483H0.4155240.5290661.717475H0.690419-1.1336521.210372H-1.7604861.2292991.858803H-1.982418-0.4115722.520165H-4.803563-1.2417580.438322H-3.614453-1.8605441.608984H-1.397651-2.3674900.895163H-0.859613-1.896094-0.736559H-4.174190-0.982413-1.844204H-2.453239-1.089113-2.312855H-3.3807951.172962-2.015826

S30

H-3.3373652.0729210.276191H-4.7510051.071563-0.168707H2.740922-1.8360541.851787H4.280793-0.9657571.773490H4.163184-2.6181021.147129H2.177642-1.874308-1.903312H2.977189-3.115218-0.938848H1.479341-2.397331-0.357505H4.355105-0.534294-1.954156H5.269156-0.284077-0.458390H5.055146-1.917591-1.096226Numberofimaginaryfrequencies=0ZPEEnergy=-919.447469FreeEnergy=-919.511185P-8+HMTA+-R6RM062X/6-311+G(d,p)(AceticAcid)11C0.405872-1.092350-0.721243C1.606744-1.967238-0.587672C2.817897-1.480025-0.302119C3.050447-0.038283-0.144647C2.0356600.831849-0.368330C0.7208470.380403-0.792086O-0.1373171.185346-1.162473C-0.505185-1.3290860.527340N-1.788281-0.6715270.393209C-2.346412-0.1845711.657779N-3.5745280.5701041.417798C-4.540533-0.2929850.734654N-4.007570-0.733983-0.556199C-2.773465-1.482539-0.328984C-3.8320620.401074-1.421306N-2.9693661.481805-0.791390C-3.3684121.7672290.648983H-1.9794421.178478-0.819503C4.4494040.4053530.253350C4.5578271.9217730.415338C4.814223-0.2586791.592774C5.440078-0.046808-0.834125H-0.171617-1.365818-1.610231H1.449100-3.037697-0.679134H3.653145-2.158141-0.177840H2.1662871.904972-0.301783H0.011654-0.9366621.408286H-0.613586-2.4135820.669932H-1.6102360.4623642.138943H-2.595519-1.0102722.340651H-5.4701460.2554900.575110

H-4.738887-1.1671961.354594H-3.034559-2.3865670.240945H-2.355207-1.785939-1.290821H-3.3454090.113425-2.352348H-4.7988000.860775-1.627555H-3.0577222.342705-1.338116H-2.5756112.3775481.079078H-4.2971212.3358790.599805H3.8770172.2963921.184574H4.3477602.446856-0.520360H5.5763382.1775760.717670H4.810556-1.3489351.528966H4.1163120.0417962.379504H5.8182990.0549941.891095H5.451820-1.131656-0.959815H6.4499060.267153-0.556033H5.1948550.407804-1.797986Numberofimaginaryfrequencies=0ZPEEnergy=-919.452385FreeEnergy=-919.517084