Dichlorophosphanyl isocyanate – spectroscopy, conformation and molecular structure in the gas phase and the solid state

文献信息

发布日期 2016-09-01

DOI 10.1039/C6CP05377G

影响因子 3.676

作者

Dingqing Li, Jan Schwabedissen, Hans-Georg Stammler, Norbert W. Mitzel, Helge Willner, Xiaoqing Zeng

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摘要

Dichlorophosphanyl isocyanate, Cl2PNCO, was synthesized and characterized by IR, Raman and 31P NMR spectroscopy. The conformational properties and molecular structures were studied by using gas electron diffraction (GED), X-ray crystallography and quantum-chemical calculations. Extensive DFT and ab initio calculations show that the potential energy surface of Cl2PNCO upon rotating the P–N bond is rather flat; three conformers, namely syn, anti and gauche between the NCO group and the bisector of the ClPCl angle, were theoretically predicted. Experimentally, only one conformer was indicated by gas-phase IR spectroscopy and the preference for a gauche conformation in both gas phase and solid state was unambiguously ascertained by gas electron diffraction and X-ray crystallographic data. In the solid state, the Cl2PNCO molecules adopt a gauche conformation with two distinct dihedral angles Cl–P–N–C of −121.3(2) and 137.4(2)° and form polymeric chains through weak intermolecular C⋯O contacts. Additionally, the dynamic character of the position of the isocyanate group of Cl2PNCO was examined in the gas phase.

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来源期刊

Physical Chemistry Chemical Physics

CiteScore: 5.5

自引率: 10.3%

年发文量: 3036

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