Diverse Reactivities of Ketones toward Compounds with Low-Valent Aluminum: Reductive Coupling, Enolization, and C═O Cleavage.

The reactivity of the α-diimine-ligated dialuminum(II) complex [LAlII-AlIIL]2- (1, dialumane, L = [(2,6-iPr2C6H3)NC(CH3)]2) and the corresponding Al(I) species [LAlI:]- (aluminyl anion) toward ketones was systematically investigated. Reaction of complex 1 with 9-fluorenone induced pinacol coupling to afford product 2 via two-electron reduction, with one electron derived from the L2- ligand and the other from the Al(II) center. In contrast, treatment of 1 with 1,3-dimethyl-2-imidazolidinone resulted in the formation of complex 3 through a simple Lewis acid-base addition. Furthermore, the Al(I) species [LAl:]-, generated via reduction of dialumane 1, reacts with benzophenone and acetophenone to yield the pinacol coupling products 4 and 5, where both electrons are donated by the Al(I) center. Notably, sterically hindered α-hydrogen-containing ketones (1,1-diphenylacetone and 2,4-dimethyl-3-pentanone) underwent enolization to form products 6 and 7 instead of C-C coupling. Compound 7 additionally involved hydrogen migration, featuring an enolized unit (OC(R)═CR'2) and an alkoxide moiety (OC(H)R2). Surprisingly, reaction of [LAl:]- with the bulkier 2,2,4,4-tetramethyl-3-pentanone led to complete C═O bond cleavage, affording product 8 via ligand-based C-C coupling and hydrogen migration from ligand L to the deoxygenated carbon. This represents the first reported instance of Group 13 elements mediating the complete cleavage of the C═O bond in ketones. The newly obtained compounds were fully characterized by EPR/NMR, IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Their electronic structures were further elucidated through DFT calculations.