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.
Hu
Jian
J
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 11754.
Xu
Huan
H
Nguyen
Minh-Hai
MH
Yip
John H K
JH
D000873:Anthracenes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010777:Photochemistry; D010782:Photolysis; D017671:Platinum Compounds / Q000737:chemistry*; D014961:X-Ray Diffraction; D000095322:Anthrones
D000873:Anthracenes; D017671:Platinum Compounds; C004522:anthrone; D000095322:Anthrones