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Photooxidation of a platinum-anthracene pincer complex: formation and structures of Pt(II)-anthrone and -ketal complexes.

Irradiating the cyclometalated pincer complex Pt(II)(DPA)Cl (1, DPA = 1,8-bis(diphenylphosphino)anthracene) in the presence of O(2) led to three sequential oxidations of the anthracenyl ring. The first photoproduct, a Pt(II)-9,10-endoperoxide complex, was converted photochemically to a Pt(II)-9-hydroxyanthrone complex A which was further oxygenated to a Pt(II)-hemiketal (B). The oxidation of A, which could be accelerated by light irradiation, probably involved a Pt(II)-anthraquinone intermediate. B underwent acid-catalyzed ketalization to form a binuclear Pt(II)(2)-diketal (B1). The photolysis was followed by UV-vis absorption and NMR spectroscopy, and the structures of A and B1 were characterized by single crystal X-ray diffraction.