Carbonyl-organocobalt(I) and -(II) complexes

Royo, Pascual; Vazquez, A.

doi:10.1016/s0022-328x(00)81479-5

Cited by 8 publications

(1 citation statement)

References 5 publications

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“…The IR spectrum of [ 1 -CO] + exhibits a medium strong band at 1854 cm –1 for the CO ligand. Compared to the stretching vibrations ranging from 1970 to 2060 cm –1 reported for the terminal Co(II)–CO moieties, − the relatively low energy of ν CO for [ 1 -CO] + suggests that the CO ligand is bridging-coordinated at the mixed-valent cobalt centers.…”

Section: Resultsmentioning

confidence: 90%

Facile Transformations of a Binuclear Cp*Co(II) Diamidonaphthalene Complex to Mixed-Valent Co(II)Co(III), Co(III)(μ-H)Co(III), and Co(III)(μ-OH)Co(III) Derivatives

et al. 2022

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A diamido-bridged dicobalt complex supported by a diamidonaphthalene ligand, Cp* 2 Co 2 (μ-1,8-C 10 H 8 (NH) 2 ) (1), was synthesized, and the reactivity relevant to redox transformations of the Co 2 N 2 core was investigated. It was found that the Co(II)− Co(II) bond allows for protonation by [HPPh 3 ][BF 4 ] resulting in a bridging hydride, [1H] + , with pK a ∼ 7.6 in CH 2 Cl 2 . The diamidonaphthalene ligand can stabilize the binuclear system in the Co(II)Co(III) mixed-valent state (1 + ), which is capable of binding CO to afford [1-CO] + . Surprisingly, the mixed-valent complex also activates H 2 O to furnish a Co(III)Co(III) hydroxy complex [1-OH] + accompanied by release of H 2 . The hydroxy ligand in [1-OH] + is exchangeable, as demonstrated by 18 O-labeling experiments on [1-OH] + with H 2 18O that led to the heavier isotopolog [1-18 OH] + .

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