Synthesis and Structural Characterization of Novel Organometallic, Rh(III), Bis(acetylacetonate) Complexes

Recently, we reported the first catalytic, intermolecular, anti-Markovnikov, hydroarylation of unactivated olefins by a homogeneous, bis-chelating, O-donor Ir(III) complex, (acac)2Ir(R)(L), based on the simplest β-diketonate, acetylacetonate, acac. With the ultimate objective of designing more active catalysts for this potentially useful reaction by structure−function studies, we embarked on developing a rational synthesis of the bis-acac Rh(III) organometallic analogues to the Ir complex. While many tris-acac, late transition metal complexes are known, no rational syntheses of bis-acac, organometallic analogues have been reported. Herein, we report the synthesis and full characterization of the organometallic complex (acac)2Rh(Ph)(CH3OH), III, and related analogues. These complexes have all been found to be air and water stable.