Stopped-flow study of the kinetics of the reaction of Rh (PPh/sub 3/) /sub 2/COC1 with cumyl and tert-butyl hydroperoxides
A spectroscopic study showed the formation of complexes of bis (triphenylphosphine) carbonylrhodium chloride with cumyl hydroperoxide (CHP) and tert-butyl hydroperoxide (TBHP) in toluene solution at 20/sup 0/C. The equilibrium constants were found for the formation of these complexes (57.5 and 160 liters/mole, respectively) at different CHP and TBHP concentrations relative to the change in intensity of the absorption bands. The stopped-flow method was used to determine the rate constants for the formation (k/sub 1/) and decomposition (k/sub 2/) of these complexes: k/sub 1/, CHP = 2.0, k/sub 1/, TBHP = 0.55 liters/mole.sec and k/sub 2/CHP = 0.035, k/sub 2/, tbhp = 0.003 sec /sup -//sub 1/. It was proposed that ternary complexes are formed upon the addition of an olefin (cyclohexane) to the bis(triphenylphosphine) carbonylrhodium chloride-CHP system.
- Research Organization:
- Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow
- OSTI ID:
- 6868248
- Journal Information:
- Kinet. Catal. (Engl. Transl.); (United States), Journal Name: Kinet. Catal. (Engl. Transl.); (United States) Vol. 27:3, PT.1; ISSN KICAA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTRA
BINDING ENERGY
CARBONIC ACID DERIVATIVES
CARBONYLS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
COMPLEXES
COMPLEXOMETRY
COORDINATION VALENCES
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
KINETICS
LEPTONS
OPACITY
OPTICAL PROPERTIES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOSGENE
PHYSICAL PROPERTIES
REACTION KINETICS
RHODIUM COMPLEXES
SPECTRA
TRANSITION ELEMENT COMPLEXES
VALENCE