†, †, †, †, †, †, †, ‡, and †(曾小庆)
†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
‡Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashihiroshima, Hiroshima 739-8526, Japan
J. Am. Chem. Soc., 2018, 140(42),13604--13608
A rare oxyphosphinidene (Me—OP) has been generated in the triplet ground state through either photolysis (266 nm) or flash-vacuum pyrolysis (FVP, 700 °C) of methoxydiazidophosphine MeOP(N3)2. Upon ArF laser irradiation (193 nm), an unprecedented isomerization from Me—OP to the long-sought methylphosphinidene oxide (Me—PO) occurs in cryogenic Ne- and N2-matrices. Alternatively, the latter can be efficiently generated through photolysis (193 nm) or FVP (ca. 700 °C) of methylphosphoryl diazide MeP(O)(N3)2, in which the elusive nitrene intermediate MeP(O)(N3)N in the triplet ground state has been also observed by IR (with 15N-labeling) and EPR (|D/hc| = 1.545 cm–1 and |E/hc| = 0.003 95 cm–1) spectroscopy.
链接:https://pubs.acs.org/doi/10.1021/jacs.8b09201