title: Gas-phase thermochemistry of ruthenium carbene metathesis catalysts.
abstract: Quantitative energy-resolved collision-induced dissociation cross-sections by tandem ESI-MS provide absolute thermochemical data for phosphine binding energies in first- and second-generation ruthenium metathesis catalysts of 33.4 and 36.9 kcal/mol, respectively. Furthermore a study of the ring-closing metathesis in the second-generation system to liberate norbornene by forming the 14-electron reactive intermediate from the intramolecular pi-complex gives an estimate of the olefin binding energy to the 14-electron complex of around 18 kcal/mol, assuming a loose transition state. The results reported here are in remarkably good agreement with the latest DFT calculations using the M06-L functional.
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich, Switzerland.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Torker
authors.forename: Daniel
authors.initials: D
authors.lastname: Merki
authors.forename: Peter
authors.initials: P
authors.lastname: Chen