Reactions of Cp*{sub 3}Co{sub 3}({mu}{sub 2}-H){sub 3}({mu}{sub 3}-H) with carbon dioxide, carbon disulfide, and phenyl isocyanate
- Univ. of Wisconsin, Madison, WI (United States)
The tetrahydride tricobalt cluster Cp {sub 3}Co{sub 3}({mu}{sub 2}-H){sub 3}({mu}{sub 3}-H) (1) reduces CO{sub 2} at 120 {degrees}C to form the dicobalt dicarbonyl complex [CpCo({mu}-CO)]{sub 2} (2) in 45% yield by H NMR. 1 reacted with CS{sub 2} at room temperature to form the thiocarbonyl cluster Cp {sub 3}Co{sub 3}({mu}{sub 3}-CS)({mu}{sup 3}-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{sub ave}=2.495 {Angstrom}] capped on one face by a {mu}{sub 3}-sulfide ligand [Co-{mu}{sub 3}-S{sub ave} = 2.129 {Angstrom}] and on the opposite face by a {mu}{sub 3}-thiocarbonyl ligand [Co-{mu}{sub 3}-C{sub ave} = 1.949, {mu}{sub 3}-C-S=1.634(5) {Angstrom}]. 1 reacted with phenyl isocyanate at 55 {degrees}C to form the N,N{prime}-diphenylureylene complex Cp {sub 2}Co{sub 2}({mu}{sub 2},{mu}{sub 2}-{eta}{sup 2}-PhNCONPh) (5), the dicarbonyl tricobalt cluster Cp {sub 3}Co{sub 3}({mu}{sub 3}-CO){sub 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 {eta}{sup 2}-N,N{prime}-diphenylureylene ligand was symmetrically bonded to cobalt atoms [Co-Co = 2.456-(1), Co-{mu}{sub 2}-N{sub ave} = 1.959 {Angstrom}].
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 457089
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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