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Steric Effects in the Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes with Coordinated Electron-Donor Alkyl Diphosphines
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    Steric Effects in the Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes with Coordinated Electron-Donor Alkyl Diphosphines
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    Dipartimento di Processi Chimici dell'Ingegneria, Università di Padova, Via F. Marzolo 9, 35131 Padova, Italy, and Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123, Venice, Italy
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    Organometallics

    Cite this: Organometallics 2007, 26, 10, 2714–2719
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    https://doi.org/10.1021/om070077x
    Published April 10, 2007
    Copyright © 2007 American Chemical Society

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    The synthesis and characterization of new hydroxo-bridged platinum(II) complexes of the type [Pt(μ-OH)(P−P)]2[BF4]2 (1ad), where P−P = R2PCH2CH2PR2 (R = Me, dmpe, 1a; Et, depe, 1b; i-Pr, dippe, 1c; Cy, dcype, 1d), and [Pt(P−P)(H2O)2][BF4]2) (where R= t-Bu, dtbpe, 1e) are reported. These complexes were tested in the Baeyer−Villiger oxidation of 2-methylcyclohexanone, 2-methylcyclopentanone, and cyclobutanone with 35% hydrogen peroxide as oxidant. The reactions were performed at 20 and 70 °C in a chlorinated solvent/H2O two-phase system. Within the above-reported series of complexes, 1e gave the highest catalytic activity and productivity in the oxidation of cyclic ketones. The Lewis acidity of 1ae was investigated through the determination of the wavenumber shift Δν̄ = ν̄(C⋮N)coord − ν̄(C⋮N)free of the isocyanide moiety in complexes of the type [PtCl(CN-2,6-(Me)2C6H3)(P−P)][BF4] (P−P = 2ae). The values of Δν̄ showed that compounds 2ae have comparable Lewis acidity, thus indicating that the difference in the catalytic activity observed for 1ae must be largely ascribed to steric requirements imparted by the alkyl diphosphine ligand.

    Copyright © 2007 American Chemical Society

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     Università di Padova.

     Università Ca' Foscari di Venezia.

    *

     Corresponding authors. E-mail:  [email protected]; [email protected].

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    This article is cited by 17 publications.

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    15. Gilberto Greggio, Paolo Sgarbossa, Alessandro Scarso, Rino A. Michelin, Giorgio Strukul. Platinum(II) diphosphine complexes as catalysts for the Baeyer–Villiger oxidation of ketones: Is it possible to increase the concentration of the active species?. Inorganica Chimica Acta 2008, 361 (11) , 3230-3236. https://doi.org/10.1016/j.ica.2007.10.042
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    17. Paolo Sgarbossa, Alessandro Scarso, Rino A. Michelin, Giorgio Strukul. Steric Effects in the Baeyer—Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes with Coordinated Electron‐Donor Alkyl Diphosphines.. ChemInform 2007, 38 (36) https://doi.org/10.1002/chin.200736030

    Organometallics

    Cite this: Organometallics 2007, 26, 10, 2714–2719
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om070077x
    Published April 10, 2007
    Copyright © 2007 American Chemical Society

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