Artículo
Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
Fecha de publicación:
11/2008
Editorial:
Elsevier Science
Revista:
Journal of Molecular Structure
ISSN:
0022-2860
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Vibrational spectra [FT IR (gas and liquid); FT Raman (liquid)] and quantum chemical calculations at different levels of theory (HF, B3LYP and MP2 using 6-31G(d), 6-311 + G(2df) and cc-pVTZ base sets) demonstrate that N-(chloroformyl) iminosulfur dichloride (ClC(O)NSCl2) is present in the fluid phases as a mixture of syn–syn and syn–anti forms (syn orientation of the CN bond with respect to the ClSCl bisector; syn or anti orientation of the carbonyl group with respect to the NS bond). From the relative IR intensities of the CO stretching bands the contribution of the syn-anti form is calculated to be 6(2)% in the gas, corresponding to a Gibbs free energy difference ΔG° = G°syn–anti − G°syn–syn = 1.6(3) kcal/mol. This value is reproduced very well by quantum chemical calculations which include electron correlation effects (ΔG° = 1.59–1.91 kcal/mol). The HF approximation overestimates this energy difference (ΔG° = 4.45 kcal/mol). On the basis of theoretical calculations and reported data for other iminosulfur dichlorides, a complete assignment of the fundamental modes for ClC(O)NSCl2 is proposed.
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Articulos(CEQUINOR)
Articulos de CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Articulos de CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Articulos(INQUINOA)
Articulos de INST.DE QUIMICA DEL NOROESTE
Articulos de INST.DE QUIMICA DEL NOROESTE
Citación
Robles, Norma Lis; Cutin, Edgardo Hugo; Alvarez, Rosa Maria Susana; Oberhammer, Heinz; Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2; Elsevier Science; Journal of Molecular Structure; 891; 1-3; 11-2008; 40-44
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