Lail, Marty Bell, Christen M. Conner, David Cundari, Thomas R. Gunnoe, T. Brent Petersen, Jeffrey L. 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. Ru;Olefins Hydroarylation reactions;benzene solution;Computational studies;activation;bond;PCP;theory calculations support;olefin insertion;styrene;CH;DFT;Computational Studies;alkyl arene;ethylbenzene;2 C 6 H 3;reaction pathway 2004-10-11
    https://acs.figshare.com/articles/journal_contribution/Experimental_and_Computational_Studies_of_Ruthenium_II_Catalyzed_Addition_of_Arene_C_H_Bonds_to_Olefins/3321427
10.1021/om049404g.s003