title: The fine balance between one cross-coupling and two beta-hydride elimination pathways: a DFT mechanistic study of Ni(pi-allyl)(2)-catalyzed cross-coupling of alkyl halides and alkyl Grignard reagents.
abstract: The model cross-coupling of EtBr with EtMgCl mediated by Ni(pi-allyl)(2) proceeds by a catalytic cycle commencing with transmetalation establishing a novel Mg-allyl interaction, followed by Mg-assisted oxidative addition (the rate-determining step), followed by reductive elimination having much lower barrier than 2 competing beta-hydride elimination pathways, and completed by departure of MgBrCl.
authors.affiliation: GIOCOMMS, 4-158 Major St., Toronto, ON, CanadaM5S 2L2. gchass@giocomms.org
authors.forename: Gregory A
authors.initials: GA
authors.lastname: Chass
authors.forename: Eric Assen B
authors.initials: EA
authors.lastname: Kantchev
authors.forename: De-Cai
authors.initials: DC
authors.lastname: Fang