title: Interfacial and intrafacial linkage isomerizations of rhenium complexes with aromatic molecules.
abstract: The mechanisms for the interconversion of facial diastereomers of a variety of TpRe(CO)(L)(eta(2)-L(Ar)) complexes [L = (t)BuNC, pyridine (py), PMe(3), or 1-methylimidazole (MeIm); L(Ar) = benzene, anisole, naphthalene, 1-methylpyrrole, furan, or thiophene; Tp = hydridotris(pyrazolyl)borate] have been investigated by (1)H NMR spin saturation experiments. In addition, the rates and free energies of activation for these processes were calculated from spin saturation experiments and T(1) measurements. The operative mechanisms for interconversion of the pi diastereomers were found to be nondissociative, undergoing either an interfacial or intrafacial linkage isomerization. A comparison of the kinetic parameters for isomerization of related eta(2)-olefin complexes of the [TpRe(CO)(PMe(3))] and [CpRe(NO)(PPh(3))](+) fragments is also presented.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, VA 22901, USA.
authors.forename: B C
authors.initials: BC
authors.lastname: Brooks
authors.forename: S H
authors.initials: SH
authors.lastname: Meiere
authors.forename: L A
authors.initials: LA
authors.lastname: Friedman
authors.forename: E H
authors.initials: EH
authors.lastname: Carrig
authors.forename: T B
authors.initials: TB
authors.lastname: Gunnoe
authors.forename: W D
authors.initials: WD
authors.lastname: Harman
mesh_terms: D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007536:Isomerism; D008968:Molecular Conformation; D012211:Rhenium / Q000737:chemistry*
chemical_list: D006841:Hydrocarbons, Aromatic; D012211:Rhenium