Phosphenic isocyanate (O2PNCO): gas-phase generation, characterization, and photodecomposition reactions

Bifeng Zhu; Junjie Jiang; Bo Lu; Xiaolong Li; Xin Jiang; Guntram Rauhut; Xiaoqing Zeng

doi:10.1039/d2cc03178g

Phosphenic isocyanate (O₂PNCO): gas-phase generation, characterization, and photodecomposition reactions

Chem Commun (Camb). 2022 Sep 22;58(76):10703-10706. doi: 10.1039/d2cc03178g.

Authors

Bifeng Zhu¹, Junjie Jiang¹, Bo Lu¹, Xiaolong Li¹, Xin Jiang¹, Guntram Rauhut², Xiaoqing Zeng¹

Affiliations

¹ Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, China. xqzeng@fudan.edu.cn.
² Institute for Theoretical Chemistry, University of Stuttgart, 70569, Stuttgart, Germany.

PMID: 36069209
DOI: 10.1039/d2cc03178g

Abstract

Phosphenic isocyanate (O₂PNCO), a novel phosphorus-containing small molecule has been generated by thermolysis of a dioxaphospholane-based precursor. The characterization of O₂PNCO with IR and UV-vis spectroscopy in solid N₂ and Ar matrices at 10 K is supported by the calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level of theory. Upon irradiation at 193 nm, O₂PNCO decomposes yielding CO₂, OPN, CO, ˙NO, and ˙PO, in which the possible formation of two exotic intermediates O₂PN and OPNO in the triplet ground state has been proposed.