Structure and Conformations of N-(Fluoroformyl)imidosulfurous Dichloride, FC(O)N=SCl2
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- 作者：Christiane Leibold ; Rosa M. S. Alvarez ; Edgardo H. Cutin ; Carlos O. Della Vedova ; and Heinz Oberhammer
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：June 30, 2003
- 年：2003
- 卷：42
- 期：13
- 页码：4071 - 4075
- 全文大小：75K
- 年卷期：v.42,no.13(June 30, 2003)
- ISSN：1520-510X
文摘
The IR (gas) and Raman (liquid) spectra of FC(O)NSCl2 demonstrate the presence of a conformational mixture inboth phases. According to a gas electron diffraction study, the main conformer (94(8)%) possesses a syn-synstructure (C(O)F group synperiplanar with respect to the SCl2 bisector and the C=O bond synperiplanar to theN=S bond). Quantum chemical calculations (HF, B3LYP and MP2 with 6-31G* basis set, and MP2/6-311(2df))predict a syn-anti structure for the second conformer. Analysis of the IR (gas) spectrum results in a contributionof 5(1)% of the minor form, corresponding to a Gibbs free energy difference 
G
= G(syn-anti) - G(syn-syn)= 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electroncorrelation effects (G = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (G= 3.24 kcal/mol).
G = G(syn-anti) - G(syn-syn)= 1.75(15) kcal/mol. This value is reproduced very well by quantum chemical calculations, which include electroncorrelation effects (G = 1.28-1.56 kcal/mol). The HF approximation overestimates this energy difference (G= 3.24 kcal/mol).