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• W2330628263 abstract "Thermolysis of the hydrogen-capped cluster HCCo2NiCp(CO)6 (1) with the redox-active diphosphine 2,3-bis(diphenylphosphino)maleic anhydride (bma) in DCE at ca. 80 °C affords the zwitterionic cluster (2) as the first observable product. Cluster 2 is not stable and transforms into the phosphido-bridged cluster (3). Both clusters 2 and 3 have been isolated and characterized in solution by IR and 31P NMR spectroscopies, and the solid-state structures of both 2 and 3 have been determined by X-ray crystallography. Cluster 2 exhibits an open Co2Ni core having one Co−Co and Co−Ni bond. The bma ligand is attached to the hydrocarbyl and CpNi moieties via the PPh2 groups, and one of the Co centers is tethered to the π bond of the bma ligand. The opened Co2Ni core of cluster 3 is structurally similar to 2 and consists of a μ2-PPh2 ligand that spans the Co−Co bond and a Ni−C σ bond resulting from the formal coupling of the maleic anhydride residue with the CpNi moiety. The reaction involving the conversion of 2 to 3 was examined by UV−vis spectroscopy and found to obey first-order kinetics. A rate-limiting step involving dissociative CO loss is supported by the rate retardation in the presence of added CO and the activation parameters (ΔH⧧ = 31.4 ± 1.2 kcal/mol and ΔS⧧ = 21 ± 4 eu). Our studies provide the first structural evidence for the attack of a phosphine ligand on the μ3-hydrocarbyl ligand in this genre of tetrahedral cluster and suggest that the nature of the capping CR group and the electrophilicity of the CpNi center play a role in determining the course of ligand substitution. Reactivity comparisons with the related bma-substituted clusters RCCo3(CO)7(bma) are discussed." @default.
• W2330628263 created "2016-06-24" @default.
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• W2330628263 date "2003-02-22" @default.
• W2330628263 modified "2023-09-26" @default.
• W2330628263 title "Phosphine Ligand Attack at Both the Methylidyne Cap and the CpNi Center in HCCo₂NiCp(CO)₆ by 2,3-Bis(diphenylphosphino)maleic Anhydride (bma): P−C Bond Cleavage Reactivity, Kinetics, and X-ray Structures of the Zwitterionic Clusters Co₂NiCp(CO)₄(μ-CO)[μ₂,η²,η¹-C(H)PPh₂CC(PPh₂)C(O)OC(O)] and Co₂NiCp(CO)₄[μ₂,η²,σ-C(H)PPh₂CCC(O)OC(O)](μ<sub>2</…" @default.
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• W2330628263 doi "https://doi.org/10.1021/om0209273" @default.
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