C–H Metalation Reaction of Diarylamine and Carbazole by Alkylaluminum Complexes at the Heteroatom‐Bridged Dimeric Aluminum Core

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<jats:title>Abstract</jats:title><jats:p>Direct metalation reactions of diphenylamine and carbazole by using an amido‐bridged dinuclear Al<jats:sub>2</jats:sub> complex proceeded across two aluminum atoms while maintaining the dinuclear structure. In contrast, an aryloxido‐bridged dinuclear aluminium complex was inert to the C–H metalation reaction. Such different reactivity of the alkylaluminum complexes with an [Al<jats:sub>2</jats:sub>O<jats:sub>2</jats:sub>] or [Al<jats:sub>2</jats:sub>N<jats:sub>2</jats:sub>] 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 Al<jats:sub>2</jats:sub>N<jats:sub>2</jats:sub> core with both a planar and butterfly shape, which creates enough space for the Al–Me moiety to activate the amines.</jats:p>

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