W. Uhl, M. Willeke, Frank Hengesbach
Oct 14, 2016
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0
Influential Citations
26
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Journal
Organometallics
Abstract
Hydroalumination or hydrogallation of a sterically encumbered hydrazone, H10C5N–N═C(C9H14) (NC5H10 = piperidine, C(C9H14) = 2-adamantdiyl), afforded hydrazides that, depending on the steric shielding by the substituents at the metal atoms, had different molecular structures. While both di(tert-butyl)metal derivatives (1a, 1b) are monomeric in the solid state with highly strained MN2 heterocycles (M = Al, Ga), the dimethylmetal compounds (1c, 1d) are dimeric with M2N2 heterocycles and exocyclic N–N bonds. The latter compounds are highly dynamic in solution. 1d crystallized as a mixture of cis- and trans-isomers as detected by crystal structure determinations. These compounds react as active Lewis pairs by their specific donor–acceptor functionality and are able to activate C–H bonds of moderately acidic substrates. Reaction of 1a (M = Al) with H–C≡C–C6H5 afforded by C–H bond activation and release of H–CMe3 trialkynyl compound 4, in which three alkynyl groups and a neutral hydrazine ligand are bound to Al....