A conformational and vibrational study of CF3 COSCH2 CH3

M.E.D. Lestard, M.E. Tuttolomondo, D.A. Wann, H.E. Robertson, D.W.H. Rankin, A. Ben Altabef

Research output: Contribution to journalArticlepeer-review


The molecular structure and conformational properties of S -ethyl trifluorothioacetate, CF3 COSCH2 CH3, were determined in the gas phase by electron diffraction and vibrational spectroscopy (IR and Raman). The experimental investigations were supplemented by ab initio (Møller Plesset of second order) and density functional theory quantum chemical calculations at different levels of theory. Both experimental and theoretical methods reveal two structures with Cs (anti, anti) and C1 (anti, gauche) symmetries, although there are disagreements about which is more stable. The electron diffraction intensities are best interpreted with a mixture of 51(3)% anti, anti and 49(3)% anti, gauche conformers. This conformational preference was studied using the total energy scheme and the natural bond orbital scheme. In addition, the infrared spectra of CF3 COSCH2 CH3 are reported for the gas, liquid and solid phases as well as the Raman spectrum of the liquid. Using calculated frequencies as a guide, evidence for both Cs and C1 structures is obtained in the IR spectra. Harmonic vibrational frequencies and scaled force fields have been calculated for both conformers. © 2009 American Institute of Physics.
Original languageUndefined/Unknown
Article number214303
JournalJournal of Chemical Physics
Issue number21
Publication statusPublished - 2009

Bibliographical note

Cited By (since 1996):3

Export Date: 1 October 2013

Source: Scopus

Art. No.: 214303


doi: 10.1063/1.3267633

PubMed ID: 19968344

Language of Original Document: English

Correspondence Address: Ben Altabef, A.; CONICET, Universidad Nacional de Tucumán Instituto de Química Del Noroeste Argentino (INQUINOA), Consejo Nacional de Investigaciones Científicas y T́cnicasArgentina; email: [email protected]

Chemicals/CAS: trifluoroacetic acid, 14477-72-6, 2923-18-4, 76-05-1; Trifluoroacetic Acid, 76-05-1; ethylthiol trifluoroacetate, 383-64-2

References: Xu, D., Prasad, K., Repic, A., Blacklock, T.J., (1995) Tetrahedron Lett., 36, p. 41. , 0040-4039; Schallenberg, E.E., Calvin, M., (1955) J. Am. Chem. Soc., 77, p. 2779. , 0002-7863. 10.1021/ja01615a032; True, N.S., Silvia, C.J., Bohn, R.K., (1981) J. Phys. Chem. A, 85, p. 1132. , 1089-5639; Defonsi Lestard, M.E., Tuttolomondo, M.E., Varetti, E.L., Wann, D.A., Robertson, H.E., Rankin, D.W.H., Ben Altabef, A., Gas-phase structure and new vibrational study of methyl trifluoroacetate, CF3 C (O) OCH3 J. Raman Spectrosc., , 0377-0486 (in press); Defonsi Lestard, M.E., Tuttolomondo, M.E., Varetti, E.L., Wann, D.A., Robertson, H.E., Rankin, D.W.H., Ben Altabef, A., Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate, CF3 CO2 CH2 CH3 J. Raman Spectrosc., , in press; Defonsi Lestard, M.E., Tuttolomondo, M.E., Varetti, E.L., Wann, D.A., Robertson, H.E., Rankin, D.W.H., Ben Altabef, A., (2009) J. Mol. Struct., 917, p. 183. , 0022-2860. 10.1016/j.molstruc.2008.08.012; Yang, W., Drueckhammer, D.G., Understanding the relative acyl-transfer reactivity of oxoesters and thioesters: Computational analysis of transition state delocalization effects (2001) Journal of the American Chemical Society, 123 (44), pp. 11004-11009. , DOI 10.1021/ja010726a; Ulic, S.E., Della Védova, C.O., Hermann, A., MacK, H.-G., Oberhammer, H., (2002) Inorg. Chem., 41, p. 5699. , 0020-1669. 10.1021/ic025659f; Shen, Q., Hagen, K., (1985) J. Mol. Struct., 128, p. 41. , 0022-2860. 10.1016/0022-2860(85)85039-0; Romano, R.M., Della Vedova, C.O., Downs, A.J., Oberhammer, H., Parsons, S., Structure and conformational properties of diacetyl sulfide in the gaseous and condensed phases explored by gas electron diffraction, single-crystal x-ray diffraction, vibrational spectroscopy, and quantum chemical calculations (2001) Journal of the American Chemical Society, 123 (50), pp. 12623-12631. , DOI 10.1021/ja0117884; MacK, H.-G., Oberhammer, H., Della Védova, C.O., (1991) J. Phys. Chem., 95, p. 4238. , 0022-3654. 10.1021/j100164a014; MacK, H.-G., Della Védova, C.O., Oberhammer, H., (1992) J. Phys. Chem., 96, p. 9215. , 0022-3654. 10.1021/j100202a028; Ulic, S.E., Kosma, A., Della Védova, C.O., Willner, H., Oberhammer, H., (2006) J. Phys. Chem., 110, p. 10201. , 0022-3654; Erben, M.F., Della Vedova, C.O., Willner, H., Trautner, F., Oberhammer, H., Boese, R., Fluoroformyl trifluoroacetyl disulfide, FC(O)SSC(O)CF3: Synthesis, structure in solid and gaseous states, and conformational properties (2005) Inorganic Chemistry, 44 (20), pp. 7070-7077. , DOI 10.1021/ic0506862; Hermann, A., Ulic, S.E., Della Vedova, C.O., MacK, H.-G., Oberhammer, H., Vibrational spectra and structures of halogencarbonyl alkyldisulfanes XC(O)SSR with X=F , Cl and R=C F3, CH3 (2001) Journal of Fluorine Chemistry, 112 (2), pp. 297-305. , DOI 10.1016/S0022-1139(01)00515-2, PII S0022113901005152; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., J. Chem. Soc. Dalton Trans., 1980, p. 954. , 0300-9246. 10.1039/dt9800000954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., J. Chem. Soc. Dalton Trans., 2005, p. 3221. , 0300-9246. 10.1039/b505287b; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., J. Chem. Soc. Dalton Trans., 2004, p. 2469. , 0300-9246. 10.1039/b407908f; (1992) International Tables for Crystallography, 100, p. 245. , A. W. Ross, M. Fink, and R. Hilderbrandt, edited by A. J. C. Wilson (Kluwer Academic, Dordrecht); http://dx.doi.org/10.1063/1.3267633, See EPAPS supplementary material at E-JCPSA6-131-043946 for experimental parameters from the GED refinement, RMSDs between experimental (GED) and calculated geometry data of C1 and Cshttp://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS), URLFrisch, M.J., Trucks, G.W., Schlegel, H.B., (2004) GAUSSIAN 03, , Revision C.02, Gaussian, Inc., Wallingford CT; Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618. , 0096-8250. 10.1103/PhysRev.46.618; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650. , 0021-9606. 10.1063/1.438955; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639. , 0021-9606. 10.1063/1.438980; Frisch, M.J., Pople, J.A., Binkley, J.S., (1984) J. Chem. Phys., 80, p. 3265. , 0021-9606. 10.1063/1.447079; Hehre, W.J., Schleyer, P.R., Pople, J.A., (1986) Ab Initio Molecular Orbital Theory, , Wiley, New York; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648. , 0021-9606. 10.1063/1.464913; Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B, 37, p. 785. , 0163-1829. 10.1103/PhysRevB.37.785; Perdew, J.P., Burke, K., Ernzerhof, M., (1996) Phys. Rev. Lett., 77, p. 3865. , 0031-9007 10.1103/PhysRevLett.77.3865; Perdew, J.P., Burke, K., Ernzerhof, M., (1997) Phys. Rev. Lett., 78, pp. 1396E. , 0031-9007 10.1103/PhysRevLett.78.1396; Sipachev, V.A., (1985) J. Mol. Struct.: THEOCHEM, 121, p. 143. , 0166-1280 10.1016/0166-1280(85)80054-3; Sipachev, V.A., Local centrifugal distortions caused by internal motions of molecules (2001) Journal of Molecular Structure, 567-568, pp. 67-72. , DOI 10.1016/S0022-2860(01)00534-8, PII S0022286001005348; Glendening, E.D., Badenhoop, J.K., Reed, A.D., Carpenter, J.E., Weinhold, F.F., (1996) Theoretical Chemistry Institute, , University of Wisconsin, Madison, WI; Fogarasi, G., Zhou, X., Taylor, P.W., Pulay, P., (1992) J. Am. Chem. Soc., 114, p. 8191. , 0002-7863. 10.1021/ja00047a032; Wilson, E.B., Decius, J.C., Cross, P.C., (1955) Molecular Vibrations, , McGraw-Hill, New York; Pulay, P., Fogarasi, G., Pongor, G., Boggs, J.E., Braga, A., (1983) J. Am. Chem. Soc., 105, p. 7037. , 0002-7863. 10.1021/ja00362a005; Collier, W.B., (1992) Program FCARTP (QCPE #631), , Department of Chemistry, Oral Roberts University, Tulsa, OK; Nielsen, B., Holder, A.J., (1997) GAUSSVIEW, User's Reference, , Gaussian, Inc., Pittsburgh, PA; Tuttolomondo, M.E., Navarro, A., Ruiz, T.P., Varetti, E.L., Hayes, S.A., Wann, D.A., Robertson, H.E., Altabef, A.B., Gas-phase structure, rotational barrier, and vibrational properties of methyl methanethiosulfonate, CH3so2SCH3: An experimental and computational study (2007) Journal of Physical Chemistry A, 111 (39), pp. 9952-9960. , DOI 10.1021/jp073611n; Duncan, J.L., (1974) Mol. Phys., 28, p. 1177. , 0026-8976. 10.1080/00268977400102501; Millefiori, S., Alparone, A., (1998) J. Chem. Soc., Faraday Trans., 94, p. 25. , 0956-5000. 10.1039/a705780f; Radom, L., Hehre, W.J., Pople, J.A., (1972) J. Am. Chem. Soc., 94, p. 2371. , 0002-7863. 10.1021/ja00762a030; Radom, L., Pople, J.A., (1970) J. Am. Chem. Soc., 92, p. 4786. , 0002-7863. 10.1021/ja00719a005; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Phys. Chem., 100, p. 12280. , 0022-3654 10.1021/jp960084r; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., J. Chem. Soc. Dalton Trans., 1996, p. 4589. , 0300-9246 10.1039/dt9960004589; Mitzel, N.W., Rankin, D.W.H., (2003) J. Chem. Soc. Dalton Trans., p. 3650. , 0300-9246 10.1039/b307022k; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502. , 0907-4449. 10.1107/S0365110X65001081; Erben, M.F., Boese, R., Della Vedova, C.O., Oberhammer, H., Willner, H., Toward an intimate understanding of the structural properties and conformational preference of oxoesters and thioesters: Gas and crystal structure and conformational analysis of dimethyl monothiocarbonate, CH 3OC(O)SCH3 (2006) Journal of Organic Chemistry, 71 (2), pp. 616-622. , DOI 10.1021/jo052026k; Gobbato, K.I., Della Védova, C.O., MacK, H.G., Oberhammer, H., (1996) Inorg. Chem., 35, p. 6152. , 0020-1669. 10.1021/ic960536e; Ulic, S.E., Coyanis, E.M., Romano, R.M., Della Védova, C.O., (1998) Spectrochim. Acta, Part A, 54, p. 695. , 0584-8539. 10.1016/S1386-1425(98)00002-X; Nagy, P.I., Tejada, F.R., Sarver, J.G., Messer, W.S., (2004) J. Phys. Chem. A, 108, p. 10173. , 1089-5639. 10.1021/jp0490251; Lynch, B.J., Truhlar, D.G., How well can hybrid density functional methods predict transition state geometries and barrier heights? (2001) Journal of Physical Chemistry A, 105 (13), pp. 2936-2941. , DOI 10.1021/jp004262z; Tuttolomondo, M.E., Navarro, A., Varetti, E.L., Ben Altabef, A., (2005) J. Raman Spectrosc., 36, p. 427. , 0377-0486. 10.1002/jrs.1316


  • Ab initio
  • Conformational preferences
  • Conformational properties
  • Experimental investigations
  • Gasphase
  • Gauche conformer
  • Harmonic vibrational frequencies
  • Infrared spectrum
  • IR spectrum
  • Natural bond orbital
  • Quantum chemical calculations
  • Raman Spectrum
  • Scaled force field
  • Second orders
  • Solid phasis
  • Total energy
  • Vibrational study
  • Chemical bonds
  • Conformations
  • Density functional theory
  • Electron diffraction
  • Liquids
  • Quantum chemistry
  • Raman spectroscopy
  • Vibrational spectroscopy
  • Infrared spectroscopy
  • drug derivative
  • ethylthiol trifluoroacetate
  • trifluoroacetic acid
  • article
  • chemical structure
  • chemistry
  • conformation
  • infrared spectrophotometry
  • quantum theory
  • Raman spectrometry
  • Models, Molecular
  • Molecular Conformation
  • Quantum Theory
  • Spectrophotometry, Infrared
  • Spectrum Analysis, Raman
  • Trifluoroacetic Acid

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