New square-planar rhodium complexes supported by the asymmetric β-ketoaminate- and bipyridine-type ligands were synthesized from dimeric rhodium(I) precursors and were characterized in solution. Oxidative addition at the rhodium(I) metal readily proceeds with a variety of substrates including halogens, alkyl halides, and acetyl halides to afford octahedral complexes of rhodium(III). While the addition of I2 and Br2 to the rhodium (I) metal generally leads to the trans addition product, the reaction with PhICl2 affords mixtures of cis and trans dichloro products with a strong solvent dependence of the isomer ratio. In contrast, the addition of 2 equivalents of silver chloride (AgCl), bromide (AgBr), and iodide (AgI) proceeds stereoselectively in all cases to afford the cis addition products of rhodium(III). The solution and solid-state structures of the cis and trans addition products will be described.

Reactivity of rhodium(I)(β-ketoaminate)(bipyridine) complexes with oxidants

251st National Meeting (2016)

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