Early History of C-H Bond Oxidative Addition

Early reports on the reactions of transition metal complexes with alkanes were published by Shilov. Sltilov and coworkers observed H/D exchanges, oxidations, and halogenations of alkanes with platinum complexes (Equation 6.20). ° Work by Crabtree and Felkin, summarized in Equations 6.21a and 6.21b, showed that soluble complexes could be used to conduct the dehydrogenation of alkanes. This body of results suggested that oxidative 

For many years, only intramolecular C-H additions were observed because this type of reaction is favored kinetically and thermodynamically. Intermolecular additions of arenes were later observed, and arenes are more reactive than alkanes toward oxidative addition to all single-metal centers. In 1982, the isolation of an alkyl hydride complex from the oxidative addition of an alkane was first reported. - Since that time, many complexes have been reported that undergo oxidative additions of alkanes. Many of these complexes do not provide stable alkyl-hydride products, but these complexes can be induced in some cases to undergo productive transformations. The following sections describe the development of intramolecular and intermolecular oxidative addition of the C-H bonds of al%l groups, aryl groups, alkanes, and arenes. 

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