10.1021/acs.inorgchem.5b02723.s007 Sivathmeehan Yogendra Sivathmeehan Yogendra Saurabh S. Chitnis Saurabh S. Chitnis Felix Hennersdorf Felix Hennersdorf Michael Bodensteiner Michael Bodensteiner Roland Fischer Roland Fischer Neil Burford Neil Burford Jan J. Weigand Jan J. Weigand Condensation Reactions of Chlorophosphanes with Chalcogenides American Chemical Society 2016 Condensation Reactions substituents R Na 2Ch Ch Reaction pathways R 2PCl reaction outcomes transition metal complexes condensation reaction sodium chalcogenides optimized protocol steric demand 2016-02-02 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Condensation_Reactions_of_Chlorophosphanes_with_Chalcogenides/2076586 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.