title: Oxygen insertion into metal carbon bonds: formation of methylperoxo Pd(II) and Pt(II) complexes via photogenerated dinuclear intermediates.
abstract: Platinum(II) and palladium(II) complexes [M(CH3)(L)]SbF6 with substituted terpyridine ligands L undergo light-driven oxygen insertion reactions into metal methyl bonds resulting in methylperoxo complexes [M(OOCH3)(L)]SbF6. The oxygen insertion reactions occur readily for complexes with methyl ligands that are activated due to steric interaction with substituents (NH2, NHMe or CH3) at the 6,6″-positions on the terpyridine ligand. All complexes exhibit attractive intermolecular π···π or M···M interactions in the solid state and in solution, which lead to excited triplet dinuclear M-M complexes upon irradiation. A mechanism is proposed whereby a dinuclear intermediate is generated upon irradiation that has a weakened M-C bond in the excited state, resulting in the observed oxygen insertion reactions.
authors.affiliation: Department of Chemistry, Imperial College London , Exhibition Road, London, SW7 2AZ, U.K.
authors.forename: Allan R
authors.initials: AR
authors.lastname: Petersen
authors.forename: Russell A
authors.initials: RA
authors.lastname: Taylor
authors.forename: Inmaculada
authors.initials: I
authors.lastname: Vicente-Hernández
authors.forename: Philip R
authors.initials: PR
authors.lastname: Mallender
authors.forename: Harriet
authors.initials: H
authors.lastname: Olley
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.forename: George J P
authors.initials: GJ
authors.lastname: Britovsek