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Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State ProductsSingle-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. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. 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. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and 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. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.
Document ID
20170000338
Acquisition Source
Glenn Research Center
Document Type
Technical Memorandum (TM)
Authors
Hepp, Aloysius F.
(NASA Glenn Research Center Cleveland, OH United States)
Kulis, Michael J.
(NASA Glenn Research Center Cleveland, OH United States)
McNatt, Jeremiah S.
(NASA Glenn Research Center Cleveland, OH United States)
Duffy, Norman V.
(Wheeling Jesuit Univ. Wheeling, WV, United States)
Hoops, Michael D.
(Wheeling Jesuit Univ. Wheeling, WV, United States)
Gorse, Elizabeth
(Maine Univ. Orono, ME, United States)
Fanwick, Philip E.
(Purdue Univ. West Lafayette, IN, United States)
Masnovi, John
(Cleveland State Univ. Cleveland, OH, United States)
Cowen, Jonathan E.
(Case Western Reserve Univ. Cleveland, OH, United States)
Dominey, Raymond N.
(Richmond Univ. VA, United States)
Date Acquired
January 11, 2017
Publication Date
December 1, 2016
Subject Category
Chemistry And Materials (General)
Inorganic, Organic And Physical Chemistry
Report/Patent Number
E-19265
NASA/TM-2016-219140
GRC-E-DAA-TN33231
Funding Number(s)
WBS: WBS 295670.01.04.56
Distribution Limits
Public
Copyright
Public Use Permitted.
Keywords
microscopy
Thermal analysis
Nickel compounds
Pyrolysis
X-ray diffraction
Spectroscopy
Crystallography
Inorganic sulfides
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