Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2,
as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric
interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogens interact with the CS2 carbons with a bond order near two; the other substituents
on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. A preliminary thermolysis study of the homoleptic species results in production of 1 : 1 nickel
sulfide phases, indicating the potential utility of these species as “single-source” precursors.
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Document Type: Research Article
Department of Chemistry, Cleveland State University, Cleveland, OH, USA
Department of Chemistry, Wheeling Jesuit University, Wheeling, WV, USA
Department of Chemistry, Purdue University, West Lafayette, IN, USA
Photovoltaics and Electrochemical Systems Branch, NASA Glenn Research Center, Cleveland, OH, USA
January 2, 2016