Condensation Reactions of Chlorophosphanes with Chalcogenides

A high-yielding and facile synthesis for diphosphane monochalcogenides (1Ch(R)) and their constitutional isomers, diphosphanylchalcoganes (2Ch(R)), was developed, featuring a condensation reaction between chlorophosphanes (R2PCl) and sodium chalcogenides (Na2Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1Ch(R) (R2(Ch)­PPR2) or 2Ch(R) (Ch­(PR2)2) depending upon the steric demand of the substituents R. Reaction pathways consistent with the distinct reaction outcomes are proposed. The application of 1Ch(R) and 2Ch(R) as an interesting class of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes.