Novel octahedral nickel(II) dithiocarbamates with bi- or tetradentate N-donor ligands: X-ray structures of [Ni(Bzppzdtc)(phen)2]ClO4 · CHCl3 and [Ni(Bz2dtc)2(cyclam)]

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]ClO4 (1), [Ni(Pe2dtc)(phen)2]ClO4 (2), [Ni(Bzppzdtc)(phen)2]ClO4 · CHCl3 (3), [Ni(Bzppzdtc)(phen)2](SCN) (4), [Ni(BzMetdtc)(bpy)2]ClO4 · 2H2O (5), [Ni(Pe2dtc)(cyclam)]ClO4 (6), [Ni(BzMetdtc)2(cyclam)] (7), [Ni(Bz2dtc)2(cyclam)] (8) and [Ni(Bz2dtc)2(phen)] (9) (BzMetdtc = N,N-benzyl-methyldithiocarbamate(1-) anion, Pe2dtc = N,N-dipentyldithiocarbamate(1-) anion, Bz2dtc = 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 N4S2 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.

Graphical abstractA series of novel octahedral nickel(II) dithiocarbamate complexes involving bidentate nitrogen-donor ligands (phen or bpy) or a tetradentate ligand (cyclam) of the composition [Ni(BzMetdtc)(phen)2]ClO4 (1), [Ni(Pe2dtc)(phen)2]ClO4 (2), [Ni(Bzppzdtc)(phen)2]ClO4 · CHCl3 (3), [Ni(Bzppzdtc)(phen)2](SCN) (4), [Ni(BzMetdtc)(bpy)2]ClO4 · 2H2O (5), [Ni(Pe2dtc)(cyclam)]ClO4 (6), [Ni(BzMetdtc)2(cyclam)] (7), [Ni(Bz2dtc)2(cyclam)] (8) and [Ni(Bz2dtc)2(phen)] (9) have been synthesized. Broad spectrum of physical techniques, including X-ray analysis of 3 and 8, proved the octahedral geometry in the vicinity of the nickel atom in all cases. The catalytic influence of complexes 2, 3, 6, and 7 on graphite oxidation was studied and discussed.Figure optionsDownload full-size imageDownload as PowerPoint slide