Nucleophilic activation of carbon monoxide. 4. Dihydrogen reduction of the methoxycarbonyl adduct Ru/sub 3/ (CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/
The anionic triruthenium cluster Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/ reacts with dihydrogen in dry THF to give methyl formate plus the hydride cluster HRu/sub 3/(CO)/sub 11//sup -/. Use of D/sub 2/ instead leads to the formation of DCO/sub 2/CH/sub 3/ plus DRu/sub 3/(CO)/sub 11//sup -/ as shown by /sup 2/H NMR. The rate of the hydrogenation is demonstrated to be first order in (H/sub 2/) but inhibited by CO. These observations are interpreted in terms of a mechanism by which the principal pathway for reduction of the cluster involves the reversible dissociation of coordinated CO followed by rate-limiting H/sub 2/ addition to the unsaturated intermediate. Details of the synthesis and spectroscopic properties of the Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/ anion are also described. 24 references, 3 figures.
- Research Organization:
- Univ. of California, Santa Barbara
- OSTI ID:
- 6868660
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:4; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
080104 -- Hydrogen-- Production-- Water Gas Processes
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
CARBONYLS
CHEMICAL REACTIONS
COMPLEXES
DATA
DEUTERIUM
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REDUCTION
RUTHENIUM COMPLEXES
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES