Methoxyphosphinidene and Isomeric Methylphosphinidene Oxide
†, †, †, †, †, †, †, ‡, 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.