Activation of alkanes by organoactinides

One year after Bergman and Graham published their work on the first definite examples of oxidative addition of an alkane CH bond, two new activation reactions of methane were reported (reactions 19 and 20). 

Watson observed by NMR the remarkable exchange of methane on the methyl lutetium complex 22 (reaction 19) [44]. Cyclohexane, which is the solvent of the reaction, does not react the linear alkanes react more slowly, but the alkyl lutetium products decompose by P hydrogen transfer. Marks et al. found that methane reacts with the thoracyclobutane 25 (obtained by thermolysis of 24) [45] to give the methyl neopentyl product 26 (reaction 20) [46]. The series of reactions 24 25 26 was 

Similarly to the oxidative addition reactions, for a long time the only intramolecular reactions known followed a multicentre pathway (a and P hydride abstractions at d metal centers are classical examples). Reactions 19 and 20 constitute the first examples of such intermolecular reactions with saturated hydrocarbons. 

In view of these recent and important advances in the field of alkane CH bond activation, the future for hydrocarbon chemistry appears particularly bright. A series of new problems arise from these discoveries. 

Most of the systems known at present give stoichiometric reactions the 

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