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

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Science  17 Jan 1992:
Vol. 255, Issue 5042, pp. 315-318
DOI: 10.1126/science.255.5042.315


The gas-phase irradiation of CpRh(CO)2 (Cp = η5-C5H5) 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.