The sulfur-bridged dimeric dithiolato rhenium(V) chelate ( D), derived from 2-mercaptothiophenol, was monomerized to give ( M− L) in benzene upon reaction with various neutral and anionic monodentate ligands ( L) such as pyridine and its substituted derivatives, triarylphosphines, dimethyl sulfoxide, 4-picoline- N-oxide, and halide ions. The kinetic observations can readily be interpreted for all ligands by a unified mechanism in which the initial fast formation of a 1:1 ( DL) and 1:2 ( DL 2) adduct is followed by the slow monomerization of each species so formed.
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The use of different ligands gave insight into different steps of the same multistep mechanism. The kinetics of ligand exchange between free L and the monomeric complexes was also studied; an associative pathway has been proposed to interpret the results. The crystal structures of two new monomeric ML complexes (with L = 4-acetylpyridine and 1,3-diethylthiourea) are reported.