Steric Effects in the Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes with Coordinated Electron-Donor Alkyl DiphosphinesClick to copy article linkArticle link copied!
Abstract

The synthesis and characterization of new hydroxo-bridged platinum(II) complexes of the type [Pt(μ-OH)(P−P)]2[BF4]2 (1a−d), 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 1a−e 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 = 2a−e). The values of Δν̄ showed that compounds 2a−e have comparable Lewis acidity, thus indicating that the difference in the catalytic activity observed for 1a−e must be largely ascribed to steric requirements imparted by the alkyl diphosphine ligand.
†
Università di Padova.
‡
Università Ca' Foscari di Venezia.
*
Corresponding authors. E-mail: [email protected]; [email protected].
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