Structural and chemical characterization of a phosphine bound M-H-M bridged carbonylate: Et4N+(.mu.-H)[Mo2(CO)9PPh3]-

Darensbourg, Marcetta Y.; Atwood, Jerry L.; Burch, R.; Hunter, William E.; Walker, N.P.

doi:10.1021/ja00504a023

Cited by 22 publications

(18 citation statements)

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“…tures. [6][7][8][9] These characteristics are contrasted to the classical ligands of organometallic chemistry, diphosphines and diimines. The results are presented herein along with an organometallic reaction principle that models steps in acetyl coA synthase as well as CO/olefin copolymerization catalysis.…”

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confidence: 99%

N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

et al. 2005

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That Cys-X-Cys tripeptide linkages can serve as tetradentate N 2 S 2 ligands, utilizing carboxamido nitrogen and cysteinyl sulfur atoms as donors in metalloenzyme active sites, has recently been verified in several protein crystal structures. [1][2][3][4][5] It was further discovered that the nickel-bound Cys-Gly-Cys NiN 2 S 2 moiety of acetyl coA synthase binds through bidentate bridging thiolate groups to a second nickel center which mediates the organometallic reactions required of the biocatalyst (the assembly of CH 3 + , CO, and SR À into the acetyl coA thioester CH 3 C( = O)SR). [1,2] The (Cys-GlyCys)Ni unit joins a host of synthetic NiN 2 S 2 complexes that are known to form multimetal clusters through m-SR interactions. Natures control of binuclearity in the construction of an organometallic catalyst presents the intriguing possibility that the NiN 2 S 2 complexes might be suitable for development as a novel class of ligands for organometalllic chemistry and catalysis. To this end we have characterized a series of NiN 2 S 2 complexes, four of which are shown in Figure 1, according to their electron-donating ability and stereochemical fea- Figure 1. NiN 2 S 2 complexes used as S-donor ligands; bme-daco = 1,5-(1,5-diazacyclooctane)di(ethylthiolate), bme*-daco = di(2-methyl-2-propylthiolate, bme-Me 2 pda = N,N'-dimethyl-2,9-diazanonanedithiolate, ema 4À = 2,7-dioxo-3,6-diazaoctanedithiolate.

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N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

et al. 2005

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“…1-3 It has become apparent from these investigations that the mononuclear group 6 metal carbnyl alkoxides are unstable with respect to aggregation to dimers or higher nuclearity clusters. This is a direct consequence of these M(CO),OR-complexes having very labile CO ligands, as demonstrated by reaction (2)…”

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confidence: 90%

Multinuclear Metal Carbonyl Alkoxide and Aryloxide Derivatives as Models for Metal Carbonyls Adsorbed on Metal Oxide Supports

Darensbourg

Mueller

Bischoff

et al. 1990

Israel Journal of Chemistry

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“…Careful and repeated analysis of mixtures of 3 a and 3 b by 1 H NMR spectroscopy revealed that the position of equilibrium at 297 K could be perturbed by photolysis with a 400 W Hg‐lamp . The first order rate constants ( k 1 +k −1 ) for the conversion of 3 b to 3 a (Figure a) were obtained by photolyzing a sample of 3 a/b in C 6 D 6 , freezing the reaction mixture immediately after the lamp was removed, transferring to an NMR spectrometer, warming to 297 K and recording the 1 H NMR spectrum as a function of time.…”

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confidence: 99%

Stereoisomerism of bis(σ‐Zincane) Complexes: Evidence for an Intramolecular Pathway

Ekkert

White

Crimmin

2017

Chemistry A European J

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The first bis(σ-zincane) complexes, heterotri- metallic species [M(CO) (η -HZnBDI) ], have been prepared (BDI=κ -{2,6-(iPr) C H NCMe} CH). For M=Cr, a single stereoisomer is observed in solution and the solid-state. For M=Mo and W, cis and trans isomers were found to reversibly interconvert at 297 K. Despite the huge steric demands of the ligand on zinc, the cis isomer was found to be the most thermodynamically stable in all cases. The activation parameters for the isomerisation when M=Mo are ΔH =20.8 kcal mol and ΔS =-12.8 cal K mol . In combination with DFT calculations, the negative activation entropy suggests an intramolecular rotation mechanism for isomerisation.

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Structural and chemical characterization of a phosphine bound M-H-M bridged carbonylate: Et4N+(.mu.-H)[Mo2(CO)9PPh3]-

Cited by 22 publications

References 8 publications

N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

Multinuclear Metal Carbonyl Alkoxide and Aryloxide Derivatives as Models for Metal Carbonyls Adsorbed on Metal Oxide Supports

Stereoisomerism of bis(σ‐Zincane) Complexes: Evidence for an Intramolecular Pathway

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Structural and chemical characterization of a phosphine bound M-H-M bridged carbonylate: Et4N+(.mu.-H)[Mo2(CO)9PPh3]-

Cited by 22 publications

References 8 publications

N2S2Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

N2S2Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

Multinuclear Metal Carbonyl Alkoxide and Aryloxide Derivatives as Models for Metal Carbonyls Adsorbed on Metal Oxide Supports

Stereoisomerism of bis(σ‐Zincane) Complexes: Evidence for an Intramolecular Pathway

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N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity

N₂S₂Ni Metallothiolates as a Class of Ligands that Support Organometallic and Bioorganometallic Reactivity