Direct metalation reactions of diphenylamine and carbazole by using an amido-bridged dinuclear Al2 complex proceeded across two aluminum atoms while maintaining the dinuclear structure. In contrast, an aryloxido-bridged dinuclear aluminum complex was inert to the C-H metalation reaction. Such different reactivity of the alkylaluminum complexes with an [Al2O2] or [Al2N2] core was attributed to the space available for the secondary amine substrates to approach the Al-Me moiety: the flexibility provided by the bridging amido ligand forms an Al2N2 core with both a planar and butterfly shape, which creates enough space for the Al-Me moiety to activate the amines. [on SciFinder(R)]
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