American Chemical Society
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A Singlet Thiophosphoryl Nitrene and Its Interconversion with Thiazyl and Thionitroso Isomers

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journal contribution
posted on 2015-09-02, 00:00 authored by Hongmin Li, Zhuang Wu, Dingqing Li, Xiaoqing Zeng, Helmut Beckers, Joseph S. Francisco
Thiophosphoryl nitrenes, R2P­(S)­N, are thiazirine-like intermediates that have been chemically inferred from trapping products in early solution studies. In this work, photolysis of the simplest thiophosphoryl azide, F2P­(S)­N3, in solid noble-gas matrices enabled a first-time spectroscopic (IR and UV–vis) identification of the thiophosphoryl nitrene F2P­(S)N in its singlet ground state. Upon visible-light irradiation (≥495 nm), it converts into the thionitroso isomer F2P–NS, which can also be produced in the gas phase from flash vacuum pyrolysis of F2P­(S)­N3. Further irradiation of F2P–NS with 365 nm UV light leads to the reformation of F2P­(S)N and isomerization to the thiazyl species F2P–SN.