om049404g_si_003.pdf (2.21 MB)
Experimental and Computational Studies of Ruthenium(II)-Catalyzed Addition of Arene C−H Bonds to Olefins
journal contribution
posted on 2004-10-11, 00:00 authored by Marty Lail, Christen M. Bell, David Conner, Thomas R. Cundari, T. Brent Gunnoe, Jeffrey L. PetersenHydroarylation reactions of olefins are catalyzed by the octahedral Ru(II) complex TpRu(CO)(NCMe)(Ph) (1) (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(PPh3)2(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-(CH2PtBu2)2C6H3) 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.