title: Binuclear complexes containing a methylnickel moiety: relevance to organonickel intermediates in acetyl coenzyme A synthase catalysis.
abstract: A series of binuclear NiNi complexes supported by a single thiolate bridge and containing a methylnickel moiety have been prepared and fully characterized. The complexes represent structural analogues for the proposed organonickel intermediate in the acetyl coenzyme A synthase catalytic cycle. Variable temperature 31P NMR spectroscopy was used to examine dynamic behavior of the thiolate bridging interaction in two of the derivatives. Kinetic analyses, independent exchange and crossover experiments support an intermolecular exchange mechanism. Carbonylation results in thioester formation via a reductive elimination pathway.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: William G
authors.initials: WG
authors.lastname: Dougherty
authors.forename: Krishnan
authors.initials: K
authors.lastname: Rangan
authors.forename: Molly J
authors.initials: MJ
authors.lastname: O'Hagan
authors.forename: Glenn P A
authors.initials: GP
authors.lastname: Yap
authors.forename: Charles G
authors.initials: CG
authors.lastname: Riordan
mesh_terms: D000106:Acetate-CoA Ligase / Q000378:metabolism*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008745:Methylation; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D055601:Organic Chemistry Phenomena
chemical_list: D009532:Nickel; D000106:Acetate-CoA Ligase
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