Experimental and Computational Studies of Ruthenium(II)-Catalyzed Addition of Arene C−H Bonds to Olefins

Hydroarylation reactions of olefins are catalyzed by the octahedral Ru(II) complex TpRu(CO)(NCMe)(Ph) (<b>1</b>) (Tp = hydridotris(pyrazolyl)borate). Experimental studies and density functional theory calculations support a reaction pathway that involves initial acetonitrile/olefin ligand exchange and subsequent olefin insertion into the ruthenium−phenyl bond. Metal-mediated C−H activation of arene to form a Ru−aryl bond with release of alkyl arene completes the proposed catalytic cycle. The cyclopentadienyl complex CpRu(PPh<sub>3</sub>)<sub>2</sub>(Ph) produces ethylbenzene and styrene from a benzene/ethylene solution at 90 °C; however, the transformation is not catalytic. A benzene solution of (PCP)Ru(CO)(Ph) (PCP = 2,6-(CH<sub>2</sub>P<sup>t</sup>Bu<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) and ethylene at 90 °C produces styrene in 12% yield without observation of ethylbenzene. Computational studies (DFT) suggest that the C−H activation step does not proceed through the formation of a Ru(IV) oxidative addition intermediate but rather occurs by a concerted pathway.