期刊
ORGANOMETALLICS
卷 32, 期 18, 页码 5008-5014出版社
AMER CHEMICAL SOC
DOI: 10.1021/om400620h
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- Deutsche Forschungsgemeinschaft
Treatment of the Al/P-based frustrated Lewis pair (FLP) Mes(2)PC(=CHPh)Al(CMe3)(2) (1) with benzaldehyde afforded the adduct 2 with a five-membered AlCPCO heterocycle. The carbonyl oxygen atom is bound to aluminum and the carbonyl carbon atom to phosphorus. 2 is dynamic in solution at room temperature, which results in a fast equilibration of the enantiomeric molecules by cleavage of the P C and fast rotation about the Al-O bond. Benzoyl chloride and 1 yielded three products (3-5). Quinoid structures were formed by C Cl bond activation, chlorine abstraction, and loss of aromaticity in the benzoyl phenyl group. Alkylation of the p-C atom by an AlCMe3 group completed the transformation and resulted concomitantly in the formation of derivatives with Al-Cl bonds. The complexes may be described as a ketene molecule coordinated to FLP 1. Benzamide reacted as a proton donor and gave cleavage of the Al C bond to the vinylic carbon atom of 1. An alkenylphosphine, Mes(2)PC(H)=C(H)CMe3, and a dinuclear amidate complex with two dialkylaluminum groups bridged by two chelating ligands were isolated.
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