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Anomeric Interactions in Pentafluoroethylimidosulfurous Dichloride, CF3CF2N=SCl2: Structural, Conformational and Configurational Properties in the Gaseous and Condensed Phases

✍ Scribed by Norma L. Robles; Rosa M. S. Álvarez; Edgardo H. Cutin; Carlos O. Della Védova; Mauricio F. Erben; Roland Boese; Helge Willner; Rüdiger Mews


Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
199 KB
Volume
2007
Category
Article
ISSN
1434-1948

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✦ Synopsis


Abstract

The structural, conformational, and configurational properties of pentafluoroethylimidosulfurous dichloride (CF~3~CF~2~N=SCl~2~) have been studied by vibrational spectroscopy [IR (vapor) and Raman (liquid)] and quantum chemical calculations [HF, B3LYP and MP2 approximations using the 6‐311+G(d) and 6‐311+G(2df) basis sets]. CF~3~CF~2~N=SCl~2~ exists in the liquid phase as a single (Z) form (C–N bond synperiplanar with respect to the Cl–S–Cl plane; C~1~ symmetry). The structure was also determined by X‐ray diffraction analysis of a single crystal grown in situ at low temperature. The crystalline solid at 159 K (monoclinic, __P__2~1~/c, a = 5.2466(10), b = 15.376(3), c = 18.730(3) Å, β = 96.391(3)°, Z = 8) consists of two crystallographically inequivalent (Z) forms. The results are discussed in terms of both hyperconjugative electronic effects and of natural bond orbital (NBO) calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)