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Issue 37, 2016
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Dichlorophosphanyl isocyanate – spectroscopy, conformation and molecular structure in the gas phase and the solid state

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Abstract

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.

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

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Publication details

The article was received on 03 Aug 2016, accepted on 01 Sep 2016 and first published on 01 Sep 2016


Article type: Paper
DOI: 10.1039/C6CP05377G
Citation: Phys. Chem. Chem. Phys., 2016,18, 26245-26253

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

    D. Li, J. Schwabedissen, H. Stammler, N. W. Mitzel, H. Willner and X. Zeng, Phys. Chem. Chem. Phys., 2016, 18, 26245
    DOI: 10.1039/C6CP05377G

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