Novel octahedral nickel(II) dithiocarbamates with bi- or tetradentate N-donor ligands: X-ray structures of [Ni(Bzppzdtc)(phen) 2]ClO 4 · CHCl 3 and [Ni(Bz 2dtc) 2(cyclam)

Abstract

A series of novel octahedral nickel(II) dithiocarbamate complexes involving bidentate nitrogen-donor ligands (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine) or a tetradentate ligand (cyclam = 1,4,8,11-tetraazacycloteradecane) of the composition [Ni(BzMetdtc)(phen) 2]ClO 4 ( 1), [Ni(Pe 2dtc)(phen) 2]ClO 4 ( 2), [Ni(Bzppzdtc)(phen) 2]ClO 4 · CHCl 3 ( 3), [Ni(Bzppzdtc)(phen) 2](SCN) ( 4), [Ni(BzMetdtc)(bpy) 2]ClO 4 · 2H 2O ( 5), [Ni(Pe 2dtc)(cyclam)]ClO 4 ( 6), [Ni(BzMetdtc) 2(cyclam)] ( 7), [Ni(Bz 2dtc) 2(cyclam)] ( 8) and [Ni(Bz 2dtc) 2(phen)] ( 9) (BzMetdtc = N, N-benzyl-methyldithiocarbamate(1-) anion, Pe 2dtc = N, N-dipentyldithiocarbamate(1-) anion, Bz 2dtc = N, N-dibenzyldithiocarbamate(1-) anion, Bzppzdtc = 4-benzylpiperazinedithiocarbamate(1-) anion), have been synthesized. Spectroscopic (electronic and infrared), magnetic moment and molar conductivity data, and thermal behaviour of the complexes are discussed. Single crystal X-ray analysis of 3 and 8 confirmed a distorted octahedral arrangement in the vicinity of the nickel atom with a N 4S 2 donor set. They represent the first X-ray structures of such type complexes. The catalytic influence of complexes 2, 3, 6, and 7 on graphite oxidation was studied and discussed.