Conformation and Structure of Dichlorophosphoryl Isocyanate in the Gaseous and Solid Phases. Issue 22 (26th July 2018)

• Record Type: Journal Article
• Authors: Schwabedissen, Jan; Li, Dingqing; Reuter, Christian G.; Stammler, Hans‐Georg; Mitzel, Norbert W.; Bernhardt, Eduard; Zeng, Xiaoqing
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 644:Issue 22(2018)
• Page Start: 1415
• Page End: 1422
• Publication Date: 2018-07-26
• Subjects: Isocyanate -- PhosphorusGas -- Gas electron diffraction -- Vibrational spectroscopy -- X‐ray diffraction -- Molecular structure -- Conformation; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201800191
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : The conformational properties and the molecular structure of dichlorophosphoryl isocyanate, Cl2 P(O)NCO, were studied by combining vibrational spectroscopy (IR and Raman), gas‐phase electron diffraction (GED), X‐ray crystallography (XRD), and quantum‐chemical calculations. Computationally, two conformers of C s symmetry with the P=O bond being in syn or anti configuration relative to the NCO group are predicted to be close in energy (ca. 2 kJ mol –1 ). Experimentally, both gas‐phase and matrix‐isolation IR spectra of Cl2 P(O)NCO suggest the presence of a single conformer, which was determined to be the energetically more favorable syn ‐conformer. This was also found to exist in the solid state by low‐temperature XRD. However, the molecule in the solid state is significantly distorted from ideal C s symmetry with an O–P–N–C dihedral angle of 38.1(1)° due to intermolecular C··· O contacts [2.881(4) Å]. In the gas phase, the GED analysis suggests that the molecule exists predominantly as syn ‐conformer but with dynamic behavior about the two minimum structures ( syn and anti ). Abstract :