Novel Copper(I) Complexes and Clusters with Phosphorus-Sulfur and Sulfur-Sulfur Containing Ligands

Abstract

The synthesis and coordination chemistry of ligands bearing PS donor groups in complexes with copper(I) halides, in particular thiophosphites, thiophosphonites, and thiophosphinites, are described.     

A Structural and Theoretical Study of the Thiophosphinite and Dithiophosphinate Anions

Two novel lithium compounds containing either the phosphorus-chalcogenide anions [Ph ₂ PS]^? or [Cy ₂ PS ₂ ]^? were isolated as decomposition products in the attempted formation of phospha(V)guanidinate anions. Lithium diphenylthiophosphinite was structurally characterized as the dimeric TMEDA adduct [Li(Ph ₂ PS)(TMEDA)] ₂ (1), in which a rare example of the κ ¹ -S bonding mode was observed for the anion. The dicyclohexyldithiophosphinate anion was incorporated into an aggregated structure with molecular formula [Li ₅ (Cy ₂ PS ₂ ) ₄ (OH)] ₂ (2). DFT calculations were performed on the isolated [R ₂ PS]^? and [R ₂ PS ₂ ]^? anions (R = Ph, Cy), indicating delocalization of electron density into the P-S bonds for each model, in agreement with bond-lengths taken from crystallographic data.