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Reactivities of activated metal carbonyl clusters. Ligand substitution kinetics of the methoxycarbonyl adduct Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00324a063· OSTI ID:6455822
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Reported are results of a kinetic study which demonstrates that the methylcarbonyl adduct Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/ is much more labile than its parent compound Ru/sub 3/(CO)/sub 12/. Reaction of the adduct with trimethylphosphite in 10/90 tetrahydrofuran/CH/sub 3/OH under CO and excess P(OCH/sub 3/)/sub 3/ produced Ru/sub 3/(CO)/sub 11/P(OCH/sub 3/)/sub 3/. A reaction mechanism is proposed. A value for the equilibrium constant has been calculated: 10.4 +- 1.15/sup -1/ at 25/sup 0/C. ..delta..H = 12 +- 2 Kcal/mol and ..delta..S = -13 +- (cal/K)/mol. The marked enhancement of the substitution lability of the trinuclear clusters upon forming the methoxycarbonyl adducts is significant. The half-life (0.0875) of the equation is 3 orders of magnitude shorter than that observed for the reaction of Ru/sub 3/(CO)/sub 12/ under analogous conditions. 16 references, 1 figure.

Research Organization:
Univ. of California, Santa Barbara
OSTI ID:
6455822
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:12; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADDUCTS
ALCOHOLS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DATA ANALYSIS
DISPERSIONS
ENTHALPY
ENTROPY
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
METHANOL
MIXED SOLVENTS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHOROUS ACID
PHYSICAL PROPERTIES
REACTION KINETICS
RUTHENIUM COMPLEXES
SOLVENTS
TETRAHYDROFURAN
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES