NASA LogoNTRSNTRS - NASA Technical Reports ServerSearchmore_vertCollectionsAboutNewsHelpLogin Back to ResultsSynthesis, 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 ID20170000338Acquisition SourceGlenn Research CenterDocument TypeTechnical Memorandum (TM)AuthorsHepp, 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 AcquiredJanuary 11, 2017Publication DateDecember 1, 2016Subject CategoryChemistry And Materials (General)Inorganic, Organic And Physical ChemistryReport/Patent NumberE-19265NASA/TM-2016-219140GRC-E-DAA-TN33231Funding Number(s)WBS: WBS 295670.01.04.56Distribution LimitsPublicCopyrightPublic Use Permitted.KeywordsmicroscopyThermal analysisNickel compoundsPyrolysisX-ray diffractionSpectroscopyCrystallographyInorganic sulfidesAvailable DownloadsNameType20170000338.pdfSTIcloud_downloadcontent_copyvisibilityRelated RecordsThere are no records associated with this record.visibility_offNo Preview Available
 No Fear Act | Freedom of Information Act | Office of the Inspector General | Agency Financial ReportsNASA Web Privacy Policy and Important Notices | NASA Guidelines for Quality of InformationDisclaimers, Copyright, Terms of Use | Accessibility | NASA OCIO | USA.gov | NASA.govContact Us | Site MapSTI LogoNASA Official: JoAnne R. Calhoun Site Curator: STI Compliance and Distribution Services Last Modified: September 12, 2024