ja5b07302_si_001.pdf (1.8 MB)
A Singlet Thiophosphoryl Nitrene and Its Interconversion with Thiazyl and Thionitroso Isomers
journal contributionposted 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–NS, 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–SN.