Organometallic chemistry of sulfur/phosphorus donor ligand complexes of nickel(II) and nickel(0)

Hsiao, Yui May; Chojnacki, Stephen S.; Hinton, Pamela S.; Reibenspies, Joseph H.; Darensbourg, Marcetta Y.

doi:10.1021/om00027a041

Cited by 62 publications

(46 citation statements)

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“…For Ni(PPh 2 CH 2 CH 2 SEt) 2+ 2 a planar structure was obtained ( Fig. 3, structure I 2+ ) which is in agreement with the crystal structure [10,15]. The one-and two-electron reduced complexes I + and I are characterized by a distorted tetrahedral coordination ( Fig.…”

Section: Nickel Complexessupporting

confidence: 78%

“…The calculations for cobalt dimethylglyoxime complexes and nickel complexes were carried out, in reference to the reactions (2) and (3). The Ni(PPh 2 CH 2 CH 2 SEt) 2 complex was examined with nickel in three oxidation states: Ni(II), Ni(I) and Ni(0) which were studied experimentally [10]. In the case of the one and two-electron reduced complex the four and three coordinated complexes were investigated.…”

Section: Methods Of Calculationsmentioning

confidence: 99%

“…A key step of such synthesis is the transfer of the methyl group from CoFeSP to the proximal Ni atom in the active site of ACS [7]. This reaction proceeds according to the equation: The occurrence of Ni(0) [8,9] or Ni(I) [10] in reaction (1) of ACS was postulated. Since the mechanism of catalytic action of the ACS enzyme is not fully understood [8,[11][12][13], models of methylation reactions involving nickel complexes and various methylation factors are being examined experimentally [9,[14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

“…Likewise, many complexes relevant to ACS enzyme are investigated experimentally [20][21][22][23][24] and computationally [25][26][27][28][29]. Examples of methylation reactions with nickel participation are [10,28]:…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study of cobalt and nickel complexes involved in methyl transfer reactions: structures, redox potentials and methyl binding energies

et al. 2019

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Cobalamins, cobalt glyoximate complexes and nickel complexes with Triphos (bis(diphenylphosphinoethyl)phenylphosphine) and PPh 2 CH 2 CH 2 SEt ligands were studied with the DFT/BP86 method in connection with methyl transfer reactions. Geometries, methyl binding energies and redox potentials were determined for the studied complexes. Three-and fourcoordinate structures were considered for nickel complex with PPh 2 CH 2 CH 2 SEt ligand, whereas four-and five-coordinate for its methyl derivative. On the basis of calculations, the possible mechanism of methyl transfer reaction between cobalt and nickel complexes was considered.

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Section: Nickel Complexessupporting

confidence: 78%

Section: Methods Of Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical study of cobalt and nickel complexes involved in methyl transfer reactions: structures, redox potentials and methyl binding energies

et al. 2019

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“…The complex undergoes two reversible n = 1 oxidations to afford the Ni I and Ni II states; the Ti IV ion is redox inactive. Similar mononuclear Ni 0 complexes with P 2 S 2 (thioether) coordination showed either irreversible oxidation [23] or a substantially larger spread in reduction potentials corresponding to the Ni II /Ni I and Ni I /Ni 0 couples [24]. …”

Section: 3 Characteristics Of Metal-metal Bondsmentioning

confidence: 99%

Metal–metal bonds in biology

Lindahl

2012

Journal of Inorganic Biochemistry

102

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Nickel-containing carbon monoxide dehydrogenases, acetyl-CoA synthases, nickel-iron hydrogenases, and diron hydrogenases are distinct metalloenzymes yet they share a number of important characteristics. All are O2-sensitive, with active-sites composed of iron and/or nickel ions coordinated primarily by sulfur ligands. In each case, two metals are juxtaposed at the “heart” of the active site, within range of forming metal-metal bonds. These active-site clusters exhibit multielectron redox abilities and must be reductively activated for catalysis. Reduction potentials are milder than expected based on formal oxidation state changes. When reductively activated, each cluster attacks an electrophilic substrate via an oxidative addition reaction. This affords a two-electron-reduced substrate bound to one or both metals of an oxidized cluster. M-M bonds have been established in hydrogenases where they serve to initiate the oxidative addition of protons and perhaps stabilize active sites in multiple redox states. The same may be true of the CODH and ACS active sites – Ni-Fe and Ni-Ni bonds in these sites may play critical roles in catalysis, stabilizing low-valence states and initiating oxidative addition of CO2 and methyl group cations, respectively. In this article, the structural and functional commonalities of these metalloenzyme active sites are described, and the case is made for the formation and use of metal-metal bonds in each enzyme mentioned. As a post-script, the importance of Fe-Fe bonds in the nitrogenase FeMoco active site is discussed.

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P−H-Functionalized 2-(Phosphanyl)ethanethiols, Their Titanocene Derivatives [Cp2Ti(SCH2CH2PHR)2] (R = Ph, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) and Reaction of [Cp2Ti(SCH2CH2PHPh)2] with [Cu(CH3CN)4]BF4

Chaudhury

Blaurock

Hey‐Hawkins

2001

Eur. J. Inorg. Chem.

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Organometallic chemistry of sulfur/phosphorus donor ligand complexes of nickel(II) and nickel(0)

Cited by 62 publications

References 0 publications

Theoretical study of cobalt and nickel complexes involved in methyl transfer reactions: structures, redox potentials and methyl binding energies

Theoretical study of cobalt and nickel complexes involved in methyl transfer reactions: structures, redox potentials and methyl binding energies

Metal–metal bonds in biology

P−H-Functionalized 2-(Phosphanyl)ethanethiols, Their Titanocene Derivatives [Cp2Ti(SCH2CH2PHR)2] (R = Ph, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) and Reaction of [Cp2Ti(SCH2CH2PHPh)2] with [Cu(CH3CN)4]BF4

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