Reactions of Cp*₃Co₃(μ₂-H)₃(μ ₃-H) with carbon dioxide, carbon bisulfide, and phenyl isocyanate

The tetrahydride tricobalt cluster Cp*3Co3(μ2-H)3(μ 3-H) (1) reduces CO2 at 120°C to form the dicobalt dicarbonyl complex [Cp*Co(μ-CO)]2 (2) in 45% yield by 1H NMR. 1 reacted with CS2 at room temperature to form the thiocarbonyl cluster Cp*3Co3(μ3-CS)(μ3-S) (3) in 19% isolated yield. 3 was characterized by X-ray crystallography and shown to consist of a triangle of cobalt atoms [Co-Co(ave) = 2.495 Å] capped on one face by μ3-sulfide ligand [Co-μ3-S(ave) = 2.129 Å] and on the opposite face by a μ3-thiocarbonyl ligand [Co-μ3-C(ave) = 1.949, μ3-C-S = 1.634(5) Å]. 1 reacted with phenyl isocyanate at 55°C to form the N,N′-diphenylureylene complex Cp*2Co2(μ2,μ2-η 2-PhNCONPh) (5), the dicarbonyl tricobalt cluster Cp*3Co3(μ3-CO)2 (6), and the carbonyl dimer 2. 5 was isolated in 13% yield and characterized by X-ray crystallography, which revealed that each nitrogen atom of the η2-N,N′-diphenylureylene ligand was symmetrically bonded to both cobalt atoms [Co-Co = 2.456-(1), Co-μ2-N(ave) = 1.959 Å]. © 1995 American Chemical Society.

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Author Ross A. Widenhoefer Chemistry