Conformational properties of F2S=N¡VCF2¡VN=SF2 and F2S=N¡VCF2¡VN=S(O)F2: Vibrational spectra and quantum chemical calculations

A. FLORES ANTOGNINI, N.L. ROBLES, E. H. CUTIN, H. OBERHAMMER

JOURNAL OF MOLECULAR STRUCTURE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2011 vol. 990 p. 33 - 45

0022-2860

The structural and conformational properties of F2Sƒ­N¡VCF2¡VNƒ­SF2 and F2Sƒ­N¡VCF2¡VNƒ­S(O)F22Sƒ­N¡VCF2¡VNƒ­SF2 and F2Sƒ­N¡VCF2¡VNƒ­S(O)F2 were studied by vibrational spectroscopy (IR(gas) and Raman(liquid)) and by quantum chemical calculations, using B3LYP and MP2 methods with small and large basis sets. Since the SF2 and S(O)F2 groups can adopt syn (s) or anti (a) position (syn/anti of the F¡VS¡VF bisector with respect to the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche S(O)F2 groups can adopt syn (s) or anti (a) position (syn/anti of the F¡VS¡VF bisector with respect to the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche 2 and S(O)F2 groups can adopt syn (s) or anti (a) position (syn/anti of the F¡VS¡VF bisector with respect to the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche 2 groups can adopt syn (s) or anti (a) position (syn/anti of the F¡VS¡VF bisector with respect to the adjacent N¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche¡VC bond) and the orientation around the two N¡VC bonds can be trans (t) or gauche (g), a large number of possible conformers is expected. In the case of F2Sƒ­N¡VCF2¡VNƒ­SF22Sƒ­N¡VCF2¡VNƒ­SF2 calculations with large basis sets predict the presence of a single conformer with both SF2 groups in2 groups in syn position and gauche orientation around both N¡VC bonds (s-g-g-s conformer). This is confirmed by the vibrational spectra. For F2Sƒ­N¡VCF2¡VNƒ­S(O)F2 analysis of the vibrational spectra in combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s by the vibrational spectra. For F2Sƒ­N¡VCF2¡VNƒ­S(O)F2 analysis of the vibrational spectra in combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s position and gauche orientation around both N¡VC bonds (s-g-g-s conformer). This is confirmed by the vibrational spectra. For F2Sƒ­N¡VCF2¡VNƒ­S(O)F2 analysis of the vibrational spectra in combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s 2Sƒ­N¡VCF2¡VNƒ­S(O)F2 analysis of the vibrational spectra in combination with the quantum chemical calculations suggests the predominance of the s-g-t-s conformer, i.e. syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s syn position of SF2 and S(O)F2 groups, gauche orientation around one N¡VC bond and trans orientation around the other N¡VC bond, and the presence of a smaller amounts of the strans orientation around the other N¡VC bond, and the presence of a smaller amounts of the s