title: Solid-state reaction study of the trans-to-cis isomerization of (eta-C(5)H(4)Me)Re(CO)[P(OPh)(3)]Br(2): a new mechanism for the isomerization reaction.
abstract: Single-crystal X-ray structures have been determined at intermediate stages in the single-crystal to single-crystal trans-to-cis thermal isomerization of (eta(5)-C(5)H(4)Me)Re(CO)[P(OPh)(3)]Br(2) at 150 degrees C. Unit cell parameters and site occupancy factors linked to the induced disorder were monitored and found to follow first-order kinetics in the initial (fast component) stage of the reaction. A rate constant of 30 x 10(-6) s(-1) (0.11 h(-1)) was obtained to first-order approximation for the reaction. The irreversibility of the isomerization from single crystals of the cis form was also confirmed. Fourier and difference Fourier maps suggest a novel 2-fold rotation mechanism for the trans-to-cis isomerization reaction. This mechanism entails a unidirectional anticlockwise movement of the CO ligand and only one Br atom.
authors.affiliation: Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa.
authors.forename: Robert S
authors.initials: RS
authors.lastname: Bogadi
authors.forename: Demetrius C
authors.initials: DC
authors.lastname: Levendis
authors.forename: Neil J
authors.initials: NJ
authors.lastname: Coville