Synthesis and characterization of mixed alpha-diimine-dithiolene complexes of group 10 metals.

摘要

Noninnocent or redox-active ligands are type of ligands where the oxidation state of metal complexes is unclear. They are several ligand types such as NO, heterodiene,phenolates, porphyrins, bis(imino)pyridines, catecholates, o-diimines, and dithiolenes are categorized into noninnocent ligands. These ligand metal complexes plays important role in developing inexpensive first row transition metals based catalysts. As well as, several metal-based biological catalytic processes involves ligand noninnocent. Recent years, utilizing modern spectroscopic techniques along with computational calculation have been used for electronic structure investigation of noninnocent complexes. Among them dithiolene and alpha-diimine complexes are prominent ones to exhibit redox activity at mild potential to form radical centered complexes. While, synthesis and electronic structure investigations of mixed &agr;-diimine-dithiolene complexes have never been carried out. In this work, we prepared and characterized mixed &agr;-diimine-dithiolene complexes of group 10 metals of the formula [(Me2C2S2)M{ArN=C(Me)C(Me)=NAr}] (M = Ni, Pd, Pt) by transmetallation reaction between [MCl2{ArN=C(Me)C(Me)=NAr}] and [(Me2C2S2)Sn(nBu)2].