Abstract
Under forcing conditions, the aluminyls [AM{Al(NON)}]2 ([NON]2− = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM2[1,4-{Al(NON)(H)}2(C6H4)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C6-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.
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