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 04:00:00 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), Journal Name: Organometallics; (United States) Vol. 13:12; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

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