A Singlet Thiophosphoryl Nitrene and Its Interconversion with Thiazyl and Thionitroso Isomers.
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.
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, China.
Hongmin
H
Li
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, China.
Zhuang
Z
Wu
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, China.
Dingqing
D
Li
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, China.
Xiaoqing
X
Zeng
Institut für Chemie und Biochemie, Freie Universität Berlin , D-14195 Berlin, Germany.
Helmut
H
Beckers
Department of Chemistry, Purdue University , West Lafayette, Indiana 47907, United States.
Joseph S
JS
Francisco
D009603:Nitroso Compounds / Q000737:chemistry*; D009946:Organothiophosphorus Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D013844:Thiazoles / Q000737:chemistry*
D009603:Nitroso Compounds; D009946:Organothiophosphorus Compounds; D013844:Thiazoles