Mononuclear NiIII alkyl complexes (Alkyl = Me and Et)

Relevance to the acetyl-CoA synthase and methyl-CoM reductase

Chien Ming Lee, Chien Hong Chen, Fu Xing Liao, Ching-Han Hu, Gene Hsiang Lee

Research output: Contribution to journalArticle

31 Citations (Scopus)

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(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/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 Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).

Original languageEnglish
Pages (from-to)9256-9258
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number27
DOIs
Publication statusPublished - 2010 Jul 14

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Acetyl Coenzyme A
Biochemistry
Protonation
SQUIDs
Bond length
Carbon Monoxide
Discrete Fourier transforms
Paramagnetic resonance
Ligands
Atmosphere
Oxidoreductases
methyl coenzyme M reductase

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Lee, Chien Ming ; Chen, Chien Hong ; Liao, Fu Xing ; Hu, Ching-Han ; Lee, Gene Hsiang. / Mononuclear NiIII alkyl complexes (Alkyl = Me and Et) : Relevance to the acetyl-CoA synthase and methyl-CoM reductase. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 27. pp. 9256-9258.
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title = "Mononuclear NiIII alkyl complexes (Alkyl = Me and Et): Relevance to the acetyl-CoA synthase and methyl-CoM reductase",
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(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/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) {\aa} in 1 and 2.015(3) {\aa} in 2 are comparable to that in the NiIII-methyl state of MCR (̃2.04 {\aa}) (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 Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).",
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Mononuclear NiIII alkyl complexes (Alkyl = Me and Et) : Relevance to the acetyl-CoA synthase and methyl-CoM reductase. / Lee, Chien Ming; Chen, Chien Hong; Liao, Fu Xing; Hu, Ching-Han; Lee, Gene Hsiang.

In: Journal of the American Chemical Society, Vol. 132, No. 27, 14.07.2010, p. 9256-9258.

Research output: Contribution to journalArticle

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T1 - Mononuclear NiIII alkyl complexes (Alkyl = Me and Et)

T2 - Relevance to the acetyl-CoA synthase and methyl-CoM reductase

AU - Lee, Chien Ming

AU - Chen, Chien Hong

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AU - Hu, Ching-Han

AU - Lee, Gene Hsiang

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N2 - 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(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/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 Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).

AB - 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(C 6H3-3-SiMe3-2-S)3)] and CH 3MgCl/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 Ni II-thiolate carbonyl [PPN][NiII(CO)(P(C6H 3-3-SiMe3-2-S)3)] (3). Additionally, protonation of 1 with phenylthiol generates NiIII-thiolate [PPN][NiIII(SPh)-(P(C6H3-3-SiMe 3-2-S)3)] (4).

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