Cationic rhodium(I) complexes of 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4) and the 6,6,13,13-tetramethyl analogue (Me4[14]aneS4). Preparation of two conformers, X-ray crystal structure of {Rh[14]aneS4}2Cl2·MeCN, and conformational effect on the nucleophilicity of the rhodium(I) ion

Abstract

Two conformers for the cationic rhodium(I) complexes of the title 14-membered cyclic tetrasulphides have been prepared and the conformational effect upon the nucleophilicity of rhodium(I) ion is shown by the oxidative addition reaction of CH₂Cl₂; {Rh[14]aneS₄}Cl (1), in which the Rh atom lies 0.1332(2)Å above the plane of four S atoms, forms a dimer through a Rh ⋯ Rh [3.313(1)Å] and four Rh ···S [3.697(9)–3.822(3)Å] intermolecular non-bonded interactions as established by an X-ray crystal structure determination.