Methoxyphosphinidene and Isomeric Methylphosphinidene Oxide

Xianxu Chu^†, Yang Yang^†, Bo Lu^†, Zhuang Wu^†, Weiyu Qian^†, Chao Song^†, Xinfang Xu^†, Manabu Abe^‡, and Xiaoqing Zeng^*†（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