Di(tert-butyl)aluminum, -gallium and -indium β-diketonates and β-diketiminates, reactions with oxygen and formation of an unprecedented peroxo-rich hexaperoxotriindium compound

Publication date: Available online 4 January 2018 Source:Journal of Organometallic Chemistry Author(s): Barun Jana, Christian Honaker, Werner Uhl Reactions of 1,3-di (tert-butyl)acetylacetone (2,2,6,6-tetramethyl-3,5-heptanedione), ( t Bu2acac)H, with tri (tert-butyl)aluminum, -gallium and -indium afforded selectively the corresponding di (tert-butyl)metal derivatives ( t Bu2acac)M t Bu2 [M = Al (1), Ga (2), In (3)] by release of isobutane. Likewise, diphenyl-β-diketamine [Ph–NC (Me)]2CH2, (Ph2nacnac)H, reacted with M t Bu3 to generate the compounds (Ph2nacnac)M t Bu2 [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. Graphical abstract

Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research