Condensation Reactions of Chlorophosphanes with Chalcogenides

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