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Phosphorylation of Diaminopyridines: Synthesis of a Compound Containing Both a Diphosphinoamine (P–N–P) and an Iminobiphosphine (N=P–P) Fragment



The phosphorylation of a series of diaminopyridines (2,3-, 3,4-, 2,5- and 2,6-diaminopyridine), with various molecular equivalents of chlorodiphenylphosphine in the presence of TEA has been studied. Notably, phosphorylation of 2,3- and 3,4-diaminopyridine affords compounds with diphosphinoamine (P–N–P) and iminobiphosphine (N=P–P) entities co-existing in the same molecule. Phosphorylations of 2,5- and 2,6-diaminopyridine afford compounds containing only diphosphinoamine units. The solid-state structure of three compounds has been determined including the first example of a crystallographically characterized compound containing both a diphosphinoamine group and an iminobiphosphine group in the same structure.