Condensation Reactions of Chlorophosphanes with Chalcogenides

A high-yielding and facile synthesis for diphosphane monochalcogenides (1_Ch^(R)) and their constitutional isomers, diphosphanylchalcoganes (2_Ch^(R)), was developed, featuring a condensation reaction between chlorophosphanes (R₂PCl) and sodium chalcogenides (Na₂Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1_Ch^(R) (R₂(Ch)­PPR₂) or 2_Ch^(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 1_Ch^(R) and 2_Ch^(R) as an interesting class of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes.