曾小庆教授与德国法兰克福大学Norbert W. Mitzel教授合作在Phys. Chem. Chem. Phys. 发表研究论文

Dingqing Li,^a   Jan Schwabedissen,^b   Hans-Georg Stammler,^b   Norbert W. Mitzel,*^b   Helge Willner^c and   Xiaoqing Zeng*^a （曾小庆）

 ^a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, China

^b Universität Bielefeld, Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für molekulare Materialien CM2, Universitätsstraße 25, 33615 Bielefeld, Germany

^c FB C-Anorganische Chemie, Bergische Universität Wuppertal, 42119 Wuppertal, Germany

Phys. Chem. Chem. Phys., 2016,18, 26245-26253

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.

链接：http://pubs.rsc.org/en/Content/ArticleLanding/2016/CP/C6CP05377G#!divAbstract