title: Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species.
abstract: The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson's catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Jesus E
authors.initials: JE
authors.lastname: Perea-Buceta
authors.affiliation: Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid (Spain).
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Sami
authors.initials: S
authors.lastname: Heikkinen
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Kirill
authors.initials: K
authors.lastname: Axenov
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Alistair W T
authors.initials: AW
authors.lastname: King
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Teemu
authors.initials: T
authors.lastname: Niemi
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Martin
authors.initials: M
authors.lastname: Nieger
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland).
authors.forename: Markku
authors.initials: M
authors.lastname: Leskelä
authors.affiliation: Department of Chemistry, P.O.Box 55, 00014 University of Helsinki (Finland). timo.repo@helsinki.fi.
authors.forename: Timo
authors.initials: T
authors.lastname: Repo
keywords: Wilkinson’s catalyst; density functional calculations; homogeneous hydrogenation; reaction mechanisms; rhodium(I)