Hu Chenyang, Rees Nicolas H, Pink Maren, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, UK.
Department of Chemistry, Indiana University, Bloomington, IN, USA.
Nat Chem. 2024 Nov;16(11):1855-1860. doi: 10.1038/s41557-024-01586-x. Epub 2024 Jul 15.
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, CH, OCH, Ph), are extremely reactive and need to be studied in inert gas matrices at ultralow temperatures (3-15 K). 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.
亚硝基化合物R-N=O是有机合成中常见的中间体，通常适合在有氧条件下于室温储存和处理。相比之下，含磷类似物，如R-P=O（R = OH、CH、OCH、Ph），反应活性极高，需要在超低温（3-15 K）的惰性气体基质中进行研究。这些物质被认为是有机磷化合物降解/燃烧过程中的关键中间体，有机磷化合物包括化学战剂和阻燃剂等一类化学品。在此，我们描述了在环境条件下通过使用极其庞大的胺配体分离出二配位氧化磷（III）。反应性研究表明，磷中心很容易被氧化，并且在此过程中P-O键保持完整，这一观察结果对于瞬态氧化磷（III）的假定反应性具有重要意义。
