Acceleration of CO dissociation by a heterometallic center: substitutional reactivity of Fe/sub 2/Ru(CO)/sub 12/ and FeRu/sub 2/(CO)/sub 12/
The substitutional reactivity of the mixed-metal clusters FeRu/sub 2/(CO)/sub 12/ and Fe/sub 2/Ru(CO)/sub 12/ has been investigated as a comparison to Fe/sub 3/(CO)/sub 12/ and Ru/sub 3/(CO)/sub 12/. The reactions are first order in cluster with only a very small dependence of the entering ligand (L = PPh/sub 3/ or P(OMe)/sub 3/), consistent with a dissociative interchange mechanism. The activation parameters and all other data are consistent with CO dissociation as the rate-determining step. FeRu/sub 2/(CO)/sub 12/ undergoes substitution to FeRu/sub 2/(CO)/sub 10/L/sub 2/ (both ligands substituted on ruthenium) with no evidence for a monosubstituted cluster. Substitution on Fe/sub 2/Ru(CO)/sub 12/ leads initially to Fe/sub 2/Ru(CO)/sub 11/L (substitution on ruthenium) and subsequently to Fe/sub 2/Ru(CO)/sub 10/L/sub 2/ (substitution on iron and ruthenium). CO dissociation from Fe/sub 2/Ru(CO)/sub 12/ and ReFu/sub 2/(CO)/sub 12/ occurs more rapidly than from Fe/sub 3/(CO)/sub 12/ or from Ru/sub 3/(CO)/sub 12/, suggesting a metal center effect on CO dissociation.
- Research Organization:
- Univ. at Buffalo, NY
- OSTI ID:
- 5648488
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:14; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DISSOCIATION
ENERGY
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
IRON COMPLEXES
KINETICS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
RUTHENIUM COMPLEXES
SPECTRA
TRANSITION ELEMENT COMPLEXES