Synthesis, characterization, and C–H activation reactions of novel organometallic O-donor ligated Rh(III) complexes

The synthesis and characterization of the O-donor ligated, air and water stable organometallic complexes trans- (2), and cis-(hfac-O,O)2Rh(CH3)(py) (3), trans-(hfac-O,O)2Rh(C6H5)(py) (4), cis-(hfac-O,O)2Rh(C6H5)(py) (5), and cis-(hfac-O,O)2Rh(Mes)(py) (6) (where hfac-O,O = κ2-O,O-1,1,1,5,5,5-hexafluoroacetylacetonato) are reported. These compounds are analogues to the O-donor iridium complexes that are active catalysts for the hydroarylation and C–H activation reactions as well as the bis-acetylacetonato rhodium complexes, which we recently reported. The trans-complex 2 undergoes a quantitative trans to cis isomerization in cyclohexane to form 3, which activates C–H bonds in both benzene and mesitylene to form compounds 5 and 6, respectively. All of these compounds are air and water stable and do not lead to decomposition products. Complex 5 promotes hydroarylation of styrene by benzene to generate dihydrostilbene.

Graphical abstractThe synthesis and characterization of O-donor ligated, air and water stable hfac-O,O rhodium complexes are reported. These compounds activate C–H bonds in both benzene and mesitylene and reaction with styrene leads to dihydrostilbene via a hydroarylation mechanism.Figure optionsDownload full-size imageDownload as PowerPoint slide