Conformational composition, molecular structure and decomposition of difluorophosphoryl azide in the gas phase

Physical Chemistry Chemical Physics : PCCP
Zhuang WuRaphael J F Berger

Abstract

The conformational composition, molecular structure and decomposition of difluorophosphoryl azide F2P(O)N3 in the gas phase were studied using gas electron diffraction (GED), matrix isolation IR spectroscopy, and quantum-chemical calculations, respectively. While computational methods predict only minor differences in the total energy between the two possible conformers (syn and anti), the analysis of electron diffraction data reveals the dominating abundance of the syn conformer in the gas phase at room temperature. Ab initio frequency analyses suggest that a low-frequency large-amplitude motion of the N3 group with respect to the P-N-N-N torsion is to be expected for the syn conformer. The large amplitude motion was included explicitly into the GED structure refinement procedure. It presumably contributes to a thermodynamic stabilization of the syn-conformer with respect to the anti-conformer in the gas phase at ambient temperature. Upon flash vacuum pyrolysis, this syn conformer undergoes a stepwise decomposition via the difluorophosphoryl nitrene, F2P(O)N, which features as the first experimentally observed phosphoryl nitrene that can be thermally produced in the gas phase. To reveal the reaction mechanism, quantum-chemical...Continue Reading

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Citations

May 29, 2018·Angewandte Chemie·Curt Wentrup
Jun 25, 2019·Angewandte Chemie·Xiaofang ZhaoXiaoqing Zeng
Jul 16, 2020·The Journal of Physical Chemistry. a·Sumitra GodaraManikandan Paranjothy
Feb 25, 2017·Chemical Reviews·Curt Wentrup
Dec 14, 2021·Journal of the American Chemical Society·André K EckhardtChristopher C Cummins

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