Complexes of late transition metals containing the mixed donor ligands 2,6-(RSCH_2)_2C_5H_3N (R = Ph, Me):Crystal structures of [{Cu(2,6-(PhSCH_2)_2C_5H_3N)(#mu#-X)}_2] (X = Cl, Br) and [Ni(2,6-PhSCH_20_2C_5H_3N)Br_2]

摘要

A range of NiX_2 and CuX (X = halide) complexes containing the tridentate NS_2 ligands, 2,6-bis(methylthiomethyl)pyridine (L~1) and 2,6-bis(phenylthiomethyl)pyridine (L~2) were preapred. Reaction of CuX with 1 molar equivalent of L~1 or L~2 afforded the binuclear species [{CuL(#mu#-X)}_2] (L = L~1, X = Cl; L = L~2, X = Cl, Br, I). These compounds have been characterised by IR and ~1H NMR spectroscopies, mass spectrometry and microanalysis. Crystal structure determination of [{CuL~2(#mu#-X)}_2] (X = Cl, Br) confirm the dimeric nature of these complexes through bridging halide centres, with the NS_2 ligands coordinated through their pyridyl nitrogens and one of the sulfur atoms in a bidentate manner. Reaction of NiX_2 with 1 molar equivalent of L~1 or L~2 afforded mononuclear species for [NiLX_2] (L = L~1, X = I; L = L~2, X = Br, I) and binuclar species for [NiLX_2]_2 (L = L~1, X = Cl, Br; L = L~2, X = Cl). These compounds have limited solubility and were characterised through IR and UV-Vis reflectance spectroscopies and microanaysis. The crystal structure determination of [NiL~2Br_2] confirms the compound to be monomeric with a five-coordinate, square pyramidal nickel centre.