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• W2062908760 endingPage "4546" @default.
• W2062908760 startingPage "4534" @default.
• W2062908760 abstract "New rhenium(VII or III) complexes [ReO3(PTA)2][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4]I (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)2][ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(η2-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)3, pz = pyrazolyl], [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)3–] and [ReCl2{N2C(O)Ph}(PTA)3] (7) have been prepared from the Re(VII) oxide Re2O7 (1–6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2{N2C(O)Ph}(Hpz)(PPh3)2], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re–PTA bond energy and hard–soft acid–base theory. The oxo-rhenium complexes 1–6 act as selective catalysts for the Baeyer–Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process." @default.
• W2062908760 created "2016-06-24" @default.
• W2062908760 creator A5002592621 @default.
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• W2062908760 creator A5045499776 @default.
• W2062908760 creator A5053563329 @default.
• W2062908760 creator A5081571915 @default.
• W2062908760 date "2013-03-27" @default.
• W2062908760 modified "2023-10-17" @default.
• W2062908760 title "Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer–Villiger Oxidation of Ketones" @default.
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