Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)

TY - JOUR

T1 - Gas-phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)

AU - Defonsi Lestard, M.E.

AU - Tuttolomondo, M.E.

AU - Varetti, E.L.

AU - Wann, D.A.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

AU - Altabef, A.B.

N1 - Cited By (since 1996):2 Export Date: 1 October 2013 Source: Scopus CODEN: JRSPA doi: 10.1002/jrs.2371 Language of Original Document: English Correspondence Address: Altabef, A. B.; INQUINOA, CONICET, Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucuḿan, San Lorenzo 456, T4000CAN Tucuḿan, R, Argentina; email: [email protected] References: Nelson, D.W., Owens, J., Hiraldo, D., (2001) J. Org. Chem, 66, p. 2572; Yang, J.J., Kirchmeier, R.L., Shreeve, J.M., (1998) J. Org. Chem, 63, p. 2656; Sosnovskikh, V.Y., Usachev, B.I., Sevenard, D.V., Röschenthaler, G.V., (2003) J. Org. Chem, 68, p. 7747; 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; Jones, G.I.L., Summers, T.D., Owen, N.L., (1974) J.chem.soc.,faradaytrans. 2, 70, p. 100; Robiette, A.G., Thompson, J.C., (1965) Spectrochim. Acta Part A, 21, p. 2023; Crowder, G.A., Jackson, D., (1971) Spectrochim. Acta Part A, 27, p. 1873; Pulay, P., Fogarasi, G., Pongor, G., Boggs, J.E., Braga, A., (1983) J. Am. Chem. Soc, 105, p. 7037; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans, 9, 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, 19, 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, 16, p. 2469; Ross, W., Fink, M., Hilderbrandt, R., (1992) International Tables For Crystallography, C, p. 245. , (Ed.: A. J. C. Wilson), Kluwer Academic Publishers: Dordrecht, Netherlands; (2001), http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS)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 C.02, , Gaussian, Inc., Wallingford; Møller, C., Plesset, M.S., (1934) Phys. Rev, 46, p. 618; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys, p. 72650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys, 72, p. 5639; Hehre, W.J., Schleyer Pv., R., Pople, J.A., (1986) Ab Initio Molecular Orbital Theory, , Wiley: New York; Becke, D., (1993) J. Chem. Phys, 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B, 37, p. 785; Alamo, C., Barone, V., (1998) J. Chem. Phys, 108, p. 664; Sipachev, V.A., (1985) J. Mol. Struct, 121, p. 143. , (THEOCHEM); 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: MadisonFogarasi, 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; Collier, W.B., (1992) Programfcartp, , (QCPE#631), Department of Chemistry, Oral Roberts University: Tulsa; Nielsen, B., Holder, A.J., (1997) Gauss View, User's Reference, , GAUSSIAN Inc.: Pittsburgh; Duncan, J.L., (1974) Mol. Phys, 28, p. 1177; Millefiori, S., Alparone, A., (1998) J. Chem. Soc., Faraday Trans, 94, p. 25; Radom, L., Hehre, W.J., Pople, J.A., (1972) J. Am. Chem. Soc, 94, p. 2371; Radom, L., Pople, J.A., (1970) J. Am. Chem. Soc, 92, p. 4786; Bond, D., Schleyer, P.R., (1990) J. Org. Chem, 55, p. 1003; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, 19, p. 3650; Ueda, T., Shimanouchi, T., (1968) J. Mol. Spectrosc, 28, p. 350; Redington, R.L., Lin, K.C., (1971) Spectrochim. Acta Part A, 27 A, p. 2445

PY - 2009/12

Y1 - 2009/12

N2 - The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.

AB - The molecular structure of methyl trifluoroacetate (CF3C(O)OCH3) has been determined in the gas phase from electrondiffraction data supplemented by abinitio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O)-O bond. The global minimum represents a Cs-symmetric structure in which the CF3 group has the anti orientation with respect to the CH3 group,but there is another potential minimum, much higher in energy, representing a Cs-symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six-fold decomposition in terms of a Fourier-type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF3C(O)OCH3 were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean-square deviation of 9cm-1 when comparing experimental and calculated frequencies. © 2009 John Wiley & Sons, Ltd.

KW - Ab initio calculations

KW - DFT calculations

KW - Gas electron diffraction

KW - Infrared spectra

KW - Methyl trifluoroacetate

KW - Raman spectra

U2 - 10.1002/jrs.2371

DO - 10.1002/jrs.2371

M3 - Article

SN - 0377-0486

VL - 40

SP - 2053

EP - 2062

JO - JOURNAL OF RAMAN SPECTROSCOPY

JF - JOURNAL OF RAMAN SPECTROSCOPY

IS - 12

ER -