Infrared spectra and structure of phosphorus isocyanates

Egorov, Yu. P.; Kisilenko, A. A.; Shokoi, V. A.

doi:10.1007/bf00739453

Cited by 3 publications

(4 citation statements)

References 8 publications

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“…Sample Preparation: Dichlorophosphoryl isocyanate, Cl 2 P(O)NCO, was synthesized by the reaction of PCl 5 with urethane [EtOC(O)NH 2 ] according to the literature . The volatile part of the reaction mixture was distilled by passing through three cold traps held at –20, –100, and –196 °C.…”

Section: Methodsmentioning

confidence: 99%

“…Continuing our interest in the synthesis and characterization of simple isocyanates, and azides,, herein, we report a first‐time full characterization of dichlorophosphoryl isocyanate, Cl 2 P(O)NCO, by combining vibrational spectroscopy, gas‐phase electron diffraction (GED), X‐ray crystallography (XRD), and quantum‐chemical calculations. Prior to this study, this isocyanate were only characterized by IR spectroscopy in the gas phase …”

Section: Introductionmentioning

confidence: 99%

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Conformation and Structure of Dichlorophosphoryl Isocyanate in the Gaseous and Solid Phases

Schwabedissen

Reuter

et al. 2018

Zeitschrift anorg allge chemie

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The conformational properties and the molecular structure of dichlorophosphoryl isocyanate, Cl2P(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 Cs 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 Cl2P(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 Cs 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).

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Conformation and Structure of Dichlorophosphoryl Isocyanate in the Gaseous and Solid Phases

Schwabedissen

Reuter

et al. 2018

Zeitschrift anorg allge chemie

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“…The value agrees with the previously reported value of 2258 cm À1 . 17 In contrast, this vibration appears as a very weak band at 2262 cm À1 in the Raman spectrum of liquid Cl 2 PNCO. Clearly, this frequency is blue-shifted in comparison to that of liquid P(NCO) 3 (IR: 2239 cm À1 , Raman: 2230 cm À1 ) 34 but is red-shifted in comparison to that of F 2 PNCO (gas phase IR: 2283 cm À1 , liquid Raman: 2268 cm À1 ), 13 consistent with the electronegativity order X(F) 4 X(Cl) 4 X(NCO).…”

Section: Vibrational Spectra Of CL 2 Pncomentioning

confidence: 97%

“…Only the most characteristic IR frequency for the asymmetric stretching vibration of the NCO group (2258 cm À1 ) has been mentioned. 17 Herein, we report first-time full spectroscopic and structural characterization of Cl 2 PNCO, including the vibrational spectra, conformation and molecular structures in both the gas phase and the solid state; the experimental results are analysed and interpreted with the aid of extensive quantum-chemical calculations.…”

Section: Introductionmentioning

confidence: 99%

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

Schwabedissen

Stammler

et al. 2016

Phys. Chem. Chem. Phys.

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Dichlorophosphanyl isocyanate, ClPNCO, was synthesized and characterized by IR, Raman and P 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 ClPNCO 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 ClPNCO 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 ClPNCO was examined in the gas phase.

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