Add time:08/18/2019         Source:sciencedirect.com

Reactions of 1,3-di(tert-butyl)acetylacetone (2,2,6,6-tetramethyl-3,5-heptanedione), (tBu2acac)H, with tri(tert-butyl)aluminum, -gallium and -indium afforded selectively the corresponding di(tert-butyl)metal derivatives (tBu2acac)MtBu2 [M = Al (1), Ga (2), In (3)] by release of isobutane. Likewise, diphenyl-β-diketamine [Ph–NC(Me)]2CH2, (Ph2nacnac)H, reacted with MtBu3 to generate the compounds (Ph2nacnac)MtBu2 [M = Ga (4), In (5)], which represent the first di(tert-butyl) complexes of gallium and indium with a β-diketiminato ligand. The reaction of 1 with molecular oxygen afforded an aluminum bisalkoxide (6) that is a dimer in the solid state. An indium peroxide (7) was reproducibly obtained in small quantities by the reaction of 3 with excess oxygen at 0 °C. Structure determination revealed a fascinating peroxo-rich triindium compound with four bridging and two terminal tert-butylperoxo moieties. The molecular core consists of an In3O7 skeleton. In contrast, THF/hexane solutions of 4 and 5 were stable towards oxygen, but slowly hydrolyzed on contact with water.

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