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• W4213426495 abstract "Abstract Several methods for the oxidation of the β‐diketiminate Al I complexes (BDI)Al and (BDI*)Al with O 2 , Et 3 P=O or N 2 O are presented (BDI=HC[C(Me)N(DIPP)] 2 , DIPP=2,6‐diisopropylphenyl; BDI*=HC[C( t Bu)N(DIPP)] 2 ). The selectivity of alumoxane formation depends strongly on the nature of the β‐diketiminate ligand, the experimental procedure and the solvent. The mononuclear alumoxanes (BDI)Al=O and (BDI*)Al=O are highly reactive intermediates that cannot be isolated but either aggregate to give less reactive dimers or decompose by internal C−H activation of a backbone Me group or an i Pr group. Ethereal solvents like Et2O react with alumoxanes to give (BDI)Al(OEt)OH and ethylene by β‐H elimination. In case of N 2 O oxidation, subsequent reaction with a second equivalent of N 2 O to form the hyponitrite complexes (BDI)Al(N 2 O 2 ) and (BDI*)Al(N 2 O 2 ) is observed. Details of the alumoxane formation, reactivity and decomposition have been obtained by DFT calculations. These calculations also underscore their rather bipolar character, represented by the resonance structure (BDI)Al + −O − , and estimate the σ‐ and π‐bond character of the Al=O bond at circa 76 % and 24 %, respectively." @default.
• W4213426495 created "2022-02-25" @default.
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• W4213426495 date "2022-03-04" @default.
• W4213426495 modified "2023-10-18" @default.
• W4213426495 title "Formation and Reactivity of Non‐Stabilized Monomeric Alumoxane Intermediates" @default.
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• W4213426495 doi "https://doi.org/10.1002/zaac.202200035" @default.
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