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 (Na(2)Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1(Ch)((R)) (R-2(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 I-h((R)) and 2(Ch)((R)) as an interesting dass of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes