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从单核环磷过渡金属配合物中光解还原消除白磷

Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo-P Transition Metal Complex.

作者信息

Mandla Kyle A, Moore Curtis E, Rheingold Arnold L, Figueroa Joshua S

机构信息

Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92093, USA.

出版信息

Angew Chem Int Ed Engl. 2019 Feb 4;58(6):1779-1783. doi: 10.1002/anie.201809042. Epub 2018 Nov 14.

Abstract

Elemental white phosphorus (P ) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example of photolytic reductive elimination of the tetrahedral P molecule from a mononuclear cyclo-P molybdenum complex. The latter functions as an air-stable, chemically-deactivated source of white phosphorus. The system features efficient photo-release of white phosphorus using inexpensive violet LED sources. Additionally, high-yield recapture of unspent white phosphorus by the molybdenum center can be achieved by post-photolysis heating at convenient temperatures.

摘要

元素白磷(P)是有机磷化合物的一种关键前体,这一点已得到广泛认可。然而,由于白磷具有毒性和自燃性,相关监管限制极大地限制了其可获取性。本文描述了一种基于单核环 - P钼配合物中四面体P分子光解还原消除的独特示例的白磷储存和释放新方法。后者作为白磷的一种空气稳定、化学失活的来源发挥作用。该系统具有使用廉价紫光LED光源高效光释放白磷的特点。此外,通过光解后在适宜温度下加热,钼中心可以实现未消耗白磷的高产率回收。

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