Activation of phosphorus by group 14 elements in low oxidation states

Abstract

The activation of phosphorus remains a popular and competitive area of research driven by the dual goals of finding ways to avoid the environmentally questionable P–Cl compounds applied in many industrial processes and the target of catalytic functionalization of P₄. In recent years the activation, degradation, fragmentation, and functionalization of white phosphorus by compounds with heavier main group elements have become a fertile area of research. The isolation of various carbenes and functionalized silylenes has prompted chemists to investigate their reactions with white phosphorus. The most intriguing fact in these reactions is the subtle change in the substituents may afford strikingly different compounds. For example, from the reaction of P₄ with PhC(NtBu)₂SiCl a cyclic Si₂P₂ derivative is obtained, whereas the analogous reaction with PhC(NtBu)₂SiN(SiMe₃)₂ resulted in an acyclic Si₂P₄ framework. Similar phenomena have also been observed in the carbene mediated P₄ activation. Apart from these, a new entry point into phosphorus chemistry is the gentle activation of P₄ by an alkyne analogue of tin. In this feature article we have covered the activation of phosphorus by compounds with low valent group 14 elements with special concern to the recent developments in this topic.