Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo-P4 Transition Metal Complex

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 (P4 ) 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 P4 molecule from a mononuclear cyclo-P4 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.

Keywords: main-group chemistry; molybdenum; photochemistry; photoelimination; white phosphorus.