Oxygen Insertion into Metal Carbon Bonds: Formation of Methylperoxo Pd(II) and Pt(II) Complexes via Photogenerated Dinuclear Intermediates

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• 作者：Allan R. Petersen ; Russell A. Taylor ; Inmaculada Vicente-Hern谩ndez ; Philip R. Mallender ; Harriet Olley ; Andrew J. P. White ; George J. P. Britovsek
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 8, 2014
• 年：2014
• 卷：136
• 期：40
• 页码：14089-14099
• 全文大小：626K
• ISSN：1520-5126

文摘

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鈥?positions on the terpyridine ligand. All complexes exhibit attractive intermolecular 蟺路路路蟺 or M路路路M interactions in the solid state and in solution, which lead to excited triplet dinuclear M鈥揗 complexes upon irradiation. A mechanism is proposed whereby a dinuclear intermediate is generated upon irradiation that has a weakened M鈥揅 bond in the excited state, resulting in the observed oxygen insertion reactions.