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Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes Containing Coordinated Electron-Poor Fluorinated Diphosphines
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    Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes Containing Coordinated Electron-Poor Fluorinated Diphosphines
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    Dipartimento di Processi Chimici dell'Ingegneria, Università di Padova, Via F. Marzolo 9, 35131 Padua, Italy, and Dipartimento di Chimica, Università di Venezia, Dorsoduro 2137, 30123 Venice, Italy
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    Organometallics

    Cite this: Organometallics 2005, 24, 5, 1012–1017
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    https://doi.org/10.1021/om049264a
    Published January 19, 2005
    Copyright © 2005 American Chemical Society

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    The synthesis and characterization of new hydroxo-bridged platinum(II) complexes of the type [P(μ-OH)(P−P)]2[BF4]2 (14), where P−P = (C6H5-nFn)2PCH2CH2P(C6H5-nFn)2 (n = 2 (2Fdppe) (1), 3 (3Fdppe) (2), 4 (4Fdppe) (3), 5 (dfppe) (4), are reported. These compounds have been used in the Baeyer−Villiger oxidation of 2-methylcyclohexanone using 35% hydrogen peroxide as oxidant. The reactions were performed at 25, 50, and 70 °C in a chlorinated solvent/H2O two-phase system. Among the fluorinated catalysts, complex 4 was found to be the best one in the oxidation of cyclic ketones; however, it is ineffective toward acyclic ketones. The Lewis acidity of the platinum(II) complexes with coordinated fluorinated diphosphines was investigated through the determination of the wavenumber shift Δν̄ = ν̄(C⋮N)coord − ν̄(C⋮N)free of the isocyanide group in complexes of the type [PtCl(CN-2,6-(CH3)2C6H3)(P−P)][BF4] (P−P = 2Fdppe, 3Fdppe, 4Fdppe, dfppe, dppe). This latter parameter, which represents a measure of the electrophilicity of the metal center, was then correlated to the catalytic activity of complexes 14 in the Baeyer−Villiger oxidation of ketones.

    Copyright © 2005 American Chemical Society

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     Università di Padova.

     Università di Venezia.

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    This article is cited by 29 publications.

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    14. Eric V. Johnston, Jan‐E. Bäckvall. Oxidation of Carbonyl Compounds. 2010, 353-369. https://doi.org/10.1002/9783527632039.ch10
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    29. Vimal K. Jain, Leela Jain. The chemistry of binuclear palladium(II) and platinum(II) complexes. Coordination Chemistry Reviews 2005, 249 (24) , 3075-3197. https://doi.org/10.1016/j.ccr.2005.06.020

    Organometallics

    Cite this: Organometallics 2005, 24, 5, 1012–1017
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om049264a
    Published January 19, 2005
    Copyright © 2005 American Chemical Society

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