Isotopic labeling investigation of the oxygenation of nickel-bound thiolates by molecular oxygen

Farmer, Patrick J.; Solouki, Touradj; Mills, Daniel K.; Soma, T.; Russell, David H.; Reibenspies, Joseph H.; Darensbourg, Marcetta Y.

doi:10.1021/ja00038a023

Cited by 126 publications

(121 citation statements)

References 3 publications

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“…(73,74,(78)(79)(80). Reaction of the dimer leads to the oxidation of only the terminal thiolates, consistent with their greater nucleophilicity and the mechanistic proposal that the reaction involves nucleophilic attack by thiolate S on O2 (74).…”

Section: Redox Chemistrysupporting

confidence: 67%

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

Maroney

Allan

Chohan

et al. 1996

ACS Symposium Series

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Many metalloenzymes have active sites composed of metals coordinated to S-donor ligands. Among the examples are Ni, Fe hydrogenases. These enzymes catalyze the two-electron redox chemistry of H2 and are believed to contain a heterodinuclear active site composed of a Ni center bridged to an Fe center by cysteinate ligands. The possible roles of the thiolate ligands in constructing the active site, in the redox chemistry of the active site, and in the binding of H + are discussed in the context of an overview of the results of physical studies of the enzyme and dinuclear model compounds.A large number of redox metalloproteins that employ thiolate (cysteinate) and/or sulfide as metal ligands is known (see Chapter 1). These proteins play key roles in biological redox processes including respiration and photosynthesis (e.g., ferredoxins (7,2), blue Cu proteins (3), CUA in cytochrome oxidase(4-6)) and in the oxidation or reduction of substrates (e.g., nitrogenase (7), hydrogenase (8-11), sulfite reductase (72)). Among these metalloproteins are a group of enzymes that contain Ni (13). Nickel containing redox metalloenzymes include methylcoenzyme M reductase (74), carbon monoxide dehydrogenase (COdH) (75) and most hydrogenases (leases) (8,16).Methylcoenzyme M reductase is found in methanogenic bacteria where it catalyzes the last step in methanogenesis: CH3SCH2CH2SO3-+ HS-HTP• CH4 + O3SCH2CH2S-S-HTP Me-coenzyme M It contains a unique Ni-containing tetrahydrocorphin cofactor, F430, which is involved in the reduction of the methyl group from methylcoenzyme M (a methylthioether) coupled with the formation of a disulfide involving coenzyme M and N-7-mercaptoheptonyl-0-phospho-L-threonine (thiols), a two-electron redox process. The exact role of the Ni in this enzyme is not well-known (17-19), although it is clear that the net redox chemistry involves thiolate oxidation.Carbon monoxide dehydrogenase catalyzes nature' s version of water-gas shift chemistry-the two-electron redox chemistry of CO: 0097-6156/96A)653-0074$16. 75A)

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Section: Redox Chemistrysupporting

confidence: 67%

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

Maroney

Allan

Chohan

et al. 1996

ACS Symposium Series

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“…Solvents were dried and distilled using standard methods. [26] (bme-daco)Ni, [27] (bme-dach)Ni, [18] and [(bme-daco) 2 Ni 3 ]-[Cl 2 ] [8] were synthesized according to published procedures. Anhydrous nickel() bromide (Strem), nickel() chloride hexahydrate (J.T.…”

Section: Methodsmentioning

confidence: 99%

“…[2Ϫ7] The most common composition is a trimetallic cluster complex with a slant-chair structure made of two square-planar N 2 S 2 Ni complexes, which flank a central planar S 4 [8,9] A 2:3 ratio of ZnCl 2 or CuBr to Ni-1 results in a C 3 -paddlewheel cluster with three Ni-1 units performing as bidentatebridging ligands, placing either Zn II or Cu I atoms in tetrahedral S 3 X coordination geometry (B, Scheme 1). [10,11] With an excess of Cu I Cl, an adamantane-like Ni 2 Cu 4 cluster C results; four CuCl units bridge two (bme*-daco)Ni II moieties [Ni-1*, bme*-daco ϭ N,NЈ-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane], engaging all available lone pairs on all sulfurs for coordinating to the soft Cu I metal centers.…”

Section: Introductionmentioning

confidence: 99%

The Construction of (N₂S₂)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C₄‐Paddlewheel Structure

et al. 2004

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In pursuit of an analogy between bidentate diphosphane ligands and cis-dithiolato nickel complexes, the easily prepared [bis(mercaptoethane)diazacycloheptane]nickel complex, Ni-1Ј, has been treated with Pd II and Ni II sources. With the latter, trinickel species are observed with typical slantchair structures; for palladium(ii) chloride, a basket-type structure is realized in which the floor of the basket is a PdS 4 unit and the sides are N 2 S 2 units. One chloride atom is held

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“…The angle formed between the planes, Ni(1)S 2 S 0 2 -Ni(2)S 4 is 68.24(19)°. Several compounds have been reported to have a similar structure [10,[25][26][27][28][29][30].…”

Section: Structures Of the Nickel Complexesmentioning

confidence: 99%

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

Verhagen

Beretta

Spek

et al. 2004

Inorganica Chimica Acta

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Isotopic labeling investigation of the oxygenation of nickel-bound thiolates by molecular oxygen

Cited by 126 publications

References 3 publications

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

The Construction of (N₂S₂)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C₄‐Paddlewheel Structure

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

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Isotopic labeling investigation of the oxygenation of nickel-bound thiolates by molecular oxygen

Cited by 126 publications

References 3 publications

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

Redox Metalloenzymes Featuring S-Donor Ligands Hydrogenase: A Case Study

The Construction of (N2S2)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C4‐Paddlewheel Structure

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

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The Construction of (N₂S₂)Ni−Pd Clusters: A Slant‐Chair, a Basket and a C₄‐Paddlewheel Structure