Open AccessOxygen Insertion into Metal Carbon Bonds: Formation of Methylperoxo Pd(II) and Pt(II) Complexes via Photogenerated Dinuclear Intermediates
Author(s) -
Allan R. Petersen,
Russell A. Taylor,
Inmaculada Vicente-Hernández,
Philip R. Mallender,
Harriet Olley,
Andrew J. P. White,
George J. P. Britovsek
Publication year - 2014
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/ja5055143
Subject(s) - chemistry , steric effects , photochemistry , excited state , oxygen , palladium , metal , terpyridine , insertion reaction , ligand (biochemistry) , intermolecular force , platinum , polymer chemistry , stereochemistry , molecule , catalysis , organic chemistry , physics , receptor , nuclear physics , biochemistry
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.