Bridging and Terminal Arrangement of Alkylperoxo Groups in Organoindium Peroxides

✍ Scribed by Werner Uhl; Barun Jana

• Book ID: 102165246
• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 183 KB
• Volume: 2009
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200900449

✦ Synopsis

Abstract

Treatment of bis(tert‐butyl)‐2,2,6,6‐tetramethyl‐3,5‐heptanedionatoindium, [(Me~3~C)~2~In{Me~3~C‐C(O)C(H)C(O)‐CMe~3~}] (1), with oxygen afforded the dinuclear alkylindium peroxide[(Me~3~C‐O‐O)(Me~3~C)In(μ‐OCMe~3~)~2~In{Me~3~C‐C(O)C(H)C(O)‐CMe~3~}~2~] (3) in moderate yield. Compound 3 has an oxidizing peroxo group in close proximity to an In–C bond and decomposes slowly at room temperature by quenching of these conflicting functionalities. The reaction of oxygen with the corresponding dibenzoylmethane derivative, [(Me~3~C)~2~In{H~5~C~6~‐C(O)C(H)C(O)‐C~6~H~5~}] (2), gave by ligand exchange the diperoxide [In~2~(μ‐O‐O‐CMe~3~)~2~{H~5~C~6~‐C(O)C(H)C(O)‐C~6~H~5~}~4~] (4) in which the indium atoms are terminally coordinated by chelating ligands and bridged by two peroxo groups. Diperoxide 4 does not contain In–C bonds, is thermally quite stable, and can be handled at room temperature in THF solution over several hours without decomposition. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)