SYNTHESES AND ELECTROCHEMISTRY OF METAL-COMPLEXES OF A BULKY PYRIDINE-THIOLATE LIGAND

Reactions of Li(tBuL-NS) (lithium bis(4-t-butylphenyl)-2-pyridylmethan thiolate(1-)) with MCl2 (M = Ni, Zn, Pt) afforded the respective M(tBu L-NS)(2) complexes in good yields. Treatment of CuCl2, Cu(OTf)(2) (OTf = triflate) and PdCl2(PhCN)(2) with Li(tBuL-NS) led to the formation of the dimeric compounds [Cu(tBuL-NS)Cl](2) . 2H(2)O, Cu-2(tBuL-NS)(3) (OTf) and [Pd(tBuL-NS)Cl](2), respectively. The interaction df Li-(t-B uL-NS) with [Ru(CO)(2)Cl-2](n), [Rh(COD)Cl](2) (COD = 1,5-cyclooctadie ne) and Re(CO)(5)Cl gave cis-Ru(tBuL-NS)(2)(CO)(2), Rh(tBuL-NS)(COD) a nd Re(tBuL-NS)(CO)(4), respectively. The structure of Rh(tBuL-NS)(COD) has been established by X-ray crystallography. The geometry around Rh is square planar with Rh-N and Rh-S distances of 2.114 (5) and 2.250 (2) Angstrom, respectively. Reaction of Ni(PMe3)(2)(CH3)Cl with Li(tBu L-NS) afforded Ni(tBuL-NS)(PMe3)CH3, which undergoes CO insertion to g ive the acyl complex Ni(tBuL-NS) (PMe3)(COCH3). The cyclic voltammogra m of Pt(tBuL-NS)(2) exhibits a reversible 1-electron couple al 0.3 V v s ferrocenium-ferrocene, which is assigned as the ligand-centered oxid ation. (C) 1997 Elsevier Science Ltd.