Syntheses, X-ray crystal structures, and fluxional behavior of the clusters Cp*[sub 3]Co[sub 3]([mu][sub 2]CO)([mu][sub 3]-CO)([mu]-H)[sub 2], Cp*[sub 3]Co[sub 3]([mu][sub 2]-H)([mu][sub 3]-[eta][sup 2]-HC[double bond]NCMe[sub 3]), and Cp*[sub 3]Co[sub 3]([mu][sub 2]-H)([mu][sub 3]-[eta][sup 2]-HC[double bond]NCMe[sub 2]CH[sub 2]Me)

Journal Article · Thu Dec 01 00:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00024a018· OSTI ID:6736361

Casey, C P; Widenhoefer, R A; Hallenbeck, S L; Hayashi, R K; Gavney, Jr, J A ^[1]

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1. Univ. of Wisconsin, Madison, WI (United States)

Cp*[sub 3]Co[sub 3]([mu][sub 2]-H)[sub 3]([mu][sub 3]-H) (1) reacts with 2 equiv of CO to form the 48-electron dicarbonyl dihydride cluster Cp*[sub 3]Co[sub 3]([mu][sub 2]-CO) ([mu][sub 3]CO)([mu]-H)[sub 2] (2), which was studied by X-ray crystallography. 2 consists of an equilateral triangle of cobalt atoms (Co[minus]Co = 2.476(1) angstroms) capped on each face by a [mu]-CO ligand. Line-shape analysis of the CO region in the variable temperature [sup 13]C NMR of 2 allowed the barrier for interconversion of the [mu][sub 2]- and [mu][sub 3]-CO ligands to be measured ([Delta]G[sup DDAG] = 8.6(1) kcal mol[sup [minus]1]). Cluster 2 loses H[sub 2] at 80[degrees]C ([Delta]G[sup [double dagger]] = 26(1) k cal mol[sup [minus]1]) to form the 46-electron dicarbonyl cluster Cp*[sub 3]Co[sub 3]([mu][sub 3]-CO)[sub 2] (3). 3 reacts with 5.4 atm of H[sub 2] at 80[degrees]C to form a 1.1:1 equilibrium mixture of 2 and 3 ([Delta]G = [minus]2.6(1) kcal mol[sup [minus]1]). tert-Butyl isocyanide reacts with 1 at [minus]35[degrees]C to form the bis(isocyanide) cluster Cp*[sub 3]Co[sub 3]([mu]CNCMe[sub 3])[sub 2]([mu]-H[sub 2])(10), which was observed by low-temperature [sup 1]H NMR spectroscopy. A coordinated tert-butyl isocyanide ligand rapidly inserted into a cobalt-hydrogen bond of 10 to produce the formimidoyl cluster Cp*[sub 3]Co[sub 3]([mu][sub 2]-H)([mu][sub 3]-[eta][sup 2]-CH = NCMe[sub 3]) (4). 42 refs., 6 figs., 7 tabs.

• OSTI ID: 6736361
• Journal Information: Organometallics; (United States), Vol. 13:12; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPLEXES
CHEMICAL REACTIONS
CRYSTALLOGRAPHY
INFRARED SPECTRA
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
SYNTHESIS
X-RAY DIFFRACTION
BENZENE
CARBON MONOXIDE
COMPILED DATA
HYDROGEN
SOLID CLUSTERS
AROMATICS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ELEMENTS
HYDROCARBONS
INFORMATION
MAGNETIC RESONANCE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures