Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene

作者：Bo Lü, Junjie Jiang, Lina Wang, Andrew R. Jupp, José M. Goicoechea, Zhongshu Li, Zhongshu Li, Mingfei Zhou, Xiaoqing Zeng · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c06016 · 被引用次数：8 · 研究领域：Chemical Reactions and Mechanisms、Synthesis and characterization of novel inorganic/organometallic compounds、Organophosphorus compounds synthesis

Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH 2 C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH 2 C(O)PH 2 ) in a solid N 2 -matrix at 12 K. The characterization of NH 2 C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet–visible (UV–vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and 15 N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH 2 C(O)P inserts into dihydrogen by the reformation of NH 2 C(O)PH 2 with concomitant isomerization to the more stable aminophosphaketene (NH 2 PCO). Additionally, the photoisomerization of NH 2 C(O)PH 2 to NH 2 C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH 3 and HPCO···NH 3 has been observed in the matrix.