Gas-Phase Rates of Alkane C-H Oxidative Addition to a Transient CpRh(CO) Complex

The gas-phase irradiation of CpRh(CO)$_2$ (Cp = $\eta^5$-C$_5$H$_5$) was examined in order to study the rates of reaction of the 16-electron intermediates presumed to be involved in the C-H oxidative addition of alkanes. "Naked" (unsolvated) CpRh(CO) was detected, and direct measurements o...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 1992-01, Vol.255 (5042), p.315-318
Main Authors: Wasserman, Eric P., Moore, C. Bradley, Bergman, Robert G.
Format: Article
Language:English
Subjects:
400500 - Photochemistry
ABSORPTION SPECTROSCOPY
ALKANES
ALKENES
CARBONYLS
CHEMICAL ACTIVATION
Chemical bonding
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
Chemistry
COMPLEXES
CYCLOALKENES
CYCLOPENTADIENE
DECOMPOSITION
DIENES
Exact sciences and technology
FLUIDS
GASES
General and physical chemistry
HYDROCARBONS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Irradiation
KINETICS
Line spectra
Liquids
Methane
Molecules
Organic Chemistry
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
PHOTOCHEMICAL REACTIONS
Photochemistry
PHOTOLYSIS
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
POLYENES
Reactants
REACTION INTERMEDIATES
REACTION KINETICS
RESOLUTION
RHODIUM COMPLEXES
SPECTROSCOPY
TIME RESOLUTION
TIMING PROPERTIES
TRANSITION ELEMENT COMPLEXES
Vapor phases
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Summary:The gas-phase irradiation of CpRh(CO)$_2$ (Cp = $\eta^5$-C$_5$H$_5$) was examined in order to study the rates of reaction of the 16-electron intermediates presumed to be involved in the C-H oxidative addition of alkanes. "Naked" (unsolvated) CpRh(CO) was detected, and direct measurements of the rates of reaction of this very short-lived complex with alkane C-H bonds were made. Activation of C-H bonds occurs on almost every collision for alkanes of moderate size, and intermediates in which the alkanes are bound to the metal centers, without their C-H bonds being fully broken, are implicated as intermediates in the overall reaction.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.255.5042.315