Methoxyphosphinidene and Isomeric Methylphosphinidene Oxide,Journal of the American Chemical Society

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Methoxyphosphinidene and Isomeric Methylphosphinidene Oxide
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-10-09 , DOI: 10.1021/jacs.8b09201
Xianxu Chu ₁ , Yang Yang ₁ , Bo Lu ₁ , Zhuang Wu ₁ , Weiyu Qian ₁ , Chao Song ₁ , Xinfang Xu ₁ , Manabu Abe ₂ , Xiaoqing Zeng ₁

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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.

中文翻译：

甲氧基亚膦和异构甲基亚膦氧化物

通过甲氧基二叠氮膦 MeOP(N3)2 的光解 (266 nm) 或快速真空热解 (FVP, 700 °C)，在三重基态下生成了一种罕见的氧亚膦 (Me-OP)。在 ArF 激光照射（193 nm）后，在低温 Ne 和 N2 基质中发生了前所未有的异构化，即从 Me-OP 到长期寻求的甲基亚膦氧化物 (Me-PO)。或者，后者可以通过甲基磷酰二叠氮 MeP(O)(N3)2 的光解 (193 nm) 或 FVP (ca. 700 °C) 有效产生，其中难以捉摸的氮烯中间体 MeP(O)(N3)N 在通过 IR（带有 15N 标记）和 EPR（| D/ hc| = 1.545 cm-1 和 | E/ hc| = 0.003 95 cm-1）光谱也观察到了三重基态。

更新日期：2018-10-09

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