title: Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV).
abstract: We report that SeO2 catalyzes the facile oxy-functionalization of (CO)5Re(I)-Me(delta-) with IO4(-) to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH3Se(VI) species. Furthermore, (CO)3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M-R(delta-) polarized bonds.
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA.
authors.forename: William J
authors.initials: WJ
authors.lastname: Tenn
authors.forename: Brian L
authors.initials: BL
authors.lastname: Conley
authors.forename: Claas H
authors.initials: CH
authors.lastname: Hövelmann
authors.forename: Mårten
authors.initials: M
authors.lastname: Ahlquist
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Nielsen
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Ess
authors.forename: Jonas
authors.initials: J
authors.lastname: Oxgaard
authors.forename: Steven M
authors.initials: SM
authors.lastname: Bischof
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard
authors.forename: Roy A
authors.initials: RA
authors.lastname: Periana