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Title: Mononuclear NiIII-Alkyl Complexes (Alkyl = Me and Et): Relevance to the Acetyl-CoA Synthase and Methyl-CoM Reductase
Authors: Lee, Chien-Ming;Chen, Chien-Hong;Liao, Fu-Xing;Hu, Ching-Han;Lee, Gene-Hsiang
Contributors: 化學系
Date: 2010
Issue Date: 2012-05-03T06:18:12Z
Publisher: American Chemical Society
Abstract: Mononuclear, distorted trigonal bipyramidal [PPN][NiIII(R)(P(C6H3-3-SiMe3-2-S)3)] (R = Me (1); R = Et (2)) were prepared by reaction of [PPN][NiIIICl(P(C6H3-3-SiMe3-2-S)3)] and CH3MgCl/C2H5MgCl, individually. EPR, SQUID studies as well as DFT computations reveal that the NiIII in 1 has a low-spin d7 electronic configuration in a distorted trigonal bipyramidal ligand field. The Ni−C bond lengths of 1.994(3) Å in 1 and 2.015(3) Å in 2 are comparable to that in the NiIII−methyl state of MCR (2.04 Å) (Sarangi, R.; Dey, M.; Ragsdale, S. W. Biochemistry 2009, 48, 3146). Under a CO atmosphere, CO triggers homolytic cleavage of the NiIII−CH3 bond in 1 to produce NiII−thiolate carbonyl [PPN][NiII(CO)(P(C6H3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII−thiolate [PPN][NiIII(SPh)(P(C6H3-3-SiMe3-2-S)3)] (4).
Relation: J. Am. Chem. Soc., 132(27): 9256-9258
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