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DOI: 10.1039/A802672F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3021-3028

A mechanistic study of the reductive coupling of acetone with uranium compounds

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Michel Ephritikhine, Olivier Maury, Claude Villiers, Monique Lance and Martine Nierlich

Abstract

Reaction of acetone with UCl4 and Li(Hg) in the molar ratio 2∶1∶2 afforded [Li2(thf[hair space])][UCl4(OCMe2CMe2O)] 4 via the intermediates [{UCl3(thf[hair space])2}2(µ-OCMe2CMe2O)] 1 and [Li2(thf[hair space])][{UCl4(thf[hair space])}2(µ-OCMe2CMe2O)] 3 (the coupling process). Unequivocal synthesis and characterization of these metallopinacols are presented; [{UCl3(hmpa)2}2(µ-OCMe2CMe2O)] (hmpa = hexamethylphosphoramide) was characterized by its crystal structure. Complex 1 was formed by dimerization of the ketyl radical [Cl3UOCMe2]˙, obtained itself by electron transfer from UCl3 to the ketone; the radical was trapped with Ph3SnH. Addition of LiCl to 1 gave 3 and the latter was transformed in the presence of Li(Hg) into 4 and UCl3. Tetramethylethylene was liberated after reduction of 4 with Li(Hg) in refluxing thf (the deoxygenation process).

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