title: Mono-alkylated bisphosphines as dopants for ESI-MS analysis of catalytic reactions.
abstract: Bisphosphines Ph(2)P(CH(2))(n)PPh(2) (n = 1, 2, 4, 6) may be easily monobenzylated to generate cationic phosphine/phosphonium ligands [Ph(2)P(CH(2))(n)PPh(2)CH(2)Ph](+). These ligands may be doped into a catalytic reaction involving neutral complexes with labile phosphine ligands, and replacement of a neutral phosphine with a charged analogue renders the resulting complex amenable to electrospray ionisation mass spectrometry (ESI-MS). Examination of olefin hydrogenation with Wilkinson's catalyst, RhCl(PPh(3))(3), revealed that this approach yielded rapid identification of all off-cycle solution species as well as catalyst poisons. Reactive intermediates could be generated using collision-induced dissociation (CID) of a triphenylphosphine ligand to make three-coordinate RhClP(2) species, and these react with alkenes in the gas phase to form RhClP(2)(alkene). The solution speciation and gas phase behaviour revealed by ESI-MS match closely to what is already known about the system from kinetic and NMR studies.
authors.affiliation: Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC V8W 3V6, Canada.
authors.forename: Danielle M
authors.initials: DM
authors.lastname: Chisholm
authors.forename: Allen G
authors.initials: AG
authors.lastname: Oliver
authors.forename: J Scott
authors.initials: JS
authors.lastname: McIndoe