Experimental and theoretical structure and vibrational analysis of ethyl trifluoroacetate, CF 3CO 2CH 2CH 3

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

Abstract

The molecular structure and conformational properties of ethyl trifluoroacetate, CF 3CO 2CH 2CH 3, were determined in the gas phase by electron diffraction, and vibrational spectroscopy (IRand Raman). The experimental investigations were supplemented by ab initio (MP2) and DFT quantum chemical calculations at different levels of theory. Experimental and theoretical methods result in two structures with C s (anti-anti) and C 1 (anti-gauche) symmetries, the former being slightly more stable than the latter. The electron-diffraction data are best fitted with a mixture of 56% anti-gauche and 44% anti-anti conformers. The conformational preference was also studied using the total energy scheme, and the natural bond orbital scheme. Also, the infrared spectra of CF 3CO 2CH 2CH 3 are reported for the gas, liquid and solid states, as is the Raman spectrum of the liquid. The comparison of experimental averaged IR spectra of C s and C 1 conformers provides evidence for the predicted conformations in the IR spectra. Harmonic vibrational wavenumbers and scaled force fields have been calculated for both conformers. Copyright © 2009 John Wiley & Sons, Ltd.
Original languageUndefined/Unknown
Pages (from-to)1357-1368
Number of pages12
JournalJOURNAL OF RAMAN SPECTROSCOPY
Volume41
Issue number10
DOIs
Publication statusPublished - Oct 2010

Bibliographical note

Cited By (since 1996):3

Export Date: 1 October 2013

Source: Scopus

CODEN: JRSPA

doi: 10.1002/jrs.2550

Language of Original Document: English

Correspondence Address: Ben Altabef, A.; INQUINOA, CONICET-Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN Tucumán, Argentina; email: altabef@fbqf.unt.edu.ar

References: Greene, T.W., Wuts, P.G.M., (1991) Protective Groups in Organic Synthesis, , John Wiley and Sons: New York; Mitchinson, A., Golding, B.T., Griffin, R.J., O'Sullivan, M.C., (1994) J. Chem. Soc., Chem. Commun., 116, p. 2613; True, N.S., Bohn, R.K., (1976) J. Am. Chem. Soc., 98, p. 1188; True, N.S., (1983) Chem. Phys. Lett., 101, p. 326; 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; 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. Raman Spectrosc., , in press; Hermann, A., Oberhammer, H., (2004) J. Fluorine Chem., 125, p. 917; Erben, M.F., Della Védova, C.O., Boese, R., Willner, H., Oberhammer, H., (2004) J. Phys. Chem. A, 108, p. 699; Della Védova, C.O., Boese, R., Willner, H., Leibold, C., Oberhammer, H., (2003) Inorg. Chem., 42, p. 7297; Tuttolomondo, M.E., Navarro, A., Varetti, E.L., Ben Altabef, A., (2005) J. Raman Spectrosc., 36, p. 427; Ulic, S.E., Della Védova, C.O., Hermann, A., Mack, H.G., Oberhammer, H., (2002) Inorg. Chem., 41, p. 5699; Erben, M.F., Boese, R., Della Védova, C.O., Oberhammer, H., Willner, H., (2006) J. Org. Chem., 71, p. 616; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans., p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans., p. 2469; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, C, p. 245. , Ed.: A. J. C. Wilson, Kluwer Academic Publishers: Dordrecht, Netherlands; Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2004) Gaussian 03, Revision D.01, , Gaussian, Inc.: Wallingford, CT; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software NSCCSMøller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Hehre, W.J., Van 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; Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B., 37, p. 785; Sipachev, V.A., (1985) J. Mol. Struct. (Theochem), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct, 567, p. 67; 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; 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; 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; 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; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans., p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502; Bohets, H., Van Der Veken, B.J., (1995) J. Raman Spectrosc., 26, p. 821; Rosas, R.L., Liefooghe, H.H., Laane, J., Van Der Veken, B.J., (1993) J. Raman Spectrosc., 24, p. 143; Kalincsák, F., Pongor, G., (2002) Spectrochim. Acta, 58 A, p. 999

Keywords

  • DFT calculations
  • Gas-phase electron diffraction
  • Infrared and Raman spectroscopy
  • Internal barrier to rotation

Cite this