2024年7月15日，美国印第安纳大学Jose M. Goicoechea课题组在《自然—化学》杂志发表论文，报道他们分离与表征了二配位氧化膦。

据悉，亚硝基化合物，R-N=O，是有机合成中常见的中间体，并且通常适合于在有氧条件下在室温下储存和操作。相比之下，含磷的类似物，如R-P =O (R = OH, CH3, OCH3, Ph)，反应性极强，需要在惰性气体基质中超低温(3-15 K)下进行研究。这些物种被认为是降解/合成有机磷化合物的关键中间体，有机磷化合物是一类用在包括化学战剂和阻燃剂中的化学物质。

在该研究中，该课题组描述了在室温室压条件下二配位磷(III)氧化物的分离，通过使用一个极其庞大的胺配体。反应性研究表明，磷中心可以很容易地被氧化，并且在这样做时，P-O键保持完整，这一观察结果对提出的瞬态磷(III)氧化物的反应性很有趣。

附：英文原文

Title: Isolation and characterization of a two-coordinate phosphinidene oxide

Author: Hu, Chenyang, Rees, Nicolas H., Pink, Maren, Goicoechea, Jose M.

Issue&Volume: 2024-07-15

Abstract: Nitroso compounds, R–N=O, are common intermediates in organic synthesis, and are typically amenable to storage and manipulation at ambient temperature under aerobic conditions. By contrast, phosphorus-containing analogues, such as R–P=O (R = OH, CH3, OCH3, Ph), are extremely reactive and need to be studied in inert gas matrices at ultralow temperatures (3–15K). These species are believed to be key intermediates in the degradation/combustion of organic phosphorus compounds, a class of chemicals that includes chemical warfare agents and flame retardants. Here we describe the isolation of a two-coordinate phosphorus(III) oxide under ambient conditions, enabled by the use of an extremely bulky amine ligand. Reactivity studies reveal that the phosphorus centre can be readily oxidized, and that in doing so, the P–O bond remains intact, an observation that is of interest to the proposed reactivity of transient phosphorus(III) oxides.

DOI: 10.1038/s41557-024-01586-x

Source: https://www.nature.com/articles/s41557-024-01586-x