Preparation of the [(DippNP)2(P4)2]2+-dication by the reaction of [DippNPCl]2 and a Lewis acid with P4.

The controlled activation of white phosphorus, P(4), provides a key entry point into many aspects of phosphorus chemistry. The activation and functionalization of P(4) by N-heterocyclic carbenes and carbene-like main group element fragments is of considerable current interest. In this communication, we report on the first use of a disguised bifunctional Lewis acid [DippNP](2)(2+) obtained from the cyclo-1,3-diphospha-2,4-diazane [DippNPCl](2) for P(4) functionalization. This has enabled the targeted preparation of novel mono- and dicationic phosphorus-rich clusters [(DippNP)(2)(P(4))Cl](+) and [(DippNP)(2)(P(4))(2)](+). The utilization of such a bifunctional phosphenium cation represents a rational and potentially versatile synthetic method for the assembly of large clusters using P(4) as a building block.