Unravelling White Phosphorus: Experimental and Computational Studies Reveal the Mechanisms of P₄ Hydrostannylation

The hydrostannylation of white phosphorus (P₄) allows this crucial industrial precursor to be easily transformed into useful P₁ products via direct, 'one pot' (or even catalytic) procedures. However, a thorough mechanistic understanding of this transformation has remained elusive, hindering attempts to use this rare example of successful, direct P₄ functionalization as a model for further reaction development. Here, we provide a deep and generalizable mechanistic picture for P₄ hydrostannylation by combining DFT calculations with in situ ³¹P NMR reaction monitoring and kinetic trapping of previously unobservable reaction intermediates using bulky tin hydrides. The results offer important insights into both how this reaction proceeds and why it is successful and provide implicit guidelines for future research in the field of P₄ activation.