title: Dichlorophosphanyl isocyanate - spectroscopy, conformation and molecular structure in the gas phase and the solid state.
abstract: Dichlorophosphanyl isocyanate, Cl2PNCO, was synthesized and characterized by IR, Raman and31P 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 CO contacts. Additionally, the dynamic character of the position of the isocyanate group of Cl2PNCO was examined in the gas phase.
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, China. xqzeng@suda.edu.cn.
authors.forename: Dingqing
authors.initials: D
authors.lastname: Li
authors.affiliation: Universität Bielefeld, Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für molekulare Materialien CM2, Universitätsstraße 25, 33615 Bielefeld, Germany. mitzel@uni-bielefeld.de.
authors.forename: Jan
authors.initials: J
authors.lastname: Schwabedissen
authors.affiliation: Universität Bielefeld, Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für molekulare Materialien CM2, Universitätsstraße 25, 33615 Bielefeld, Germany. mitzel@uni-bielefeld.de.
authors.forename: Hans-Georg
authors.initials: HG
authors.lastname: Stammler
authors.affiliation: Universität Bielefeld, Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie, Centrum für molekulare Materialien CM2, Universitätsstraße 25, 33615 Bielefeld, Germany. mitzel@uni-bielefeld.de.
authors.forename: Norbert W
authors.initials: NW
authors.lastname: Mitzel
authors.affiliation: FB C-Anorganische Chemie, Bergische Universität Wuppertal, 42119 Wuppertal, Germany.
authors.forename: Helge
authors.initials: H
authors.lastname: Willner
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, China. xqzeng@suda.edu.cn.
authors.forename: Xiaoqing
authors.initials: X
authors.lastname: Zeng