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.