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The π(C=C) HOMO energies of 2-methyl-2-pentene, 3-methyl-2-buten-1-ol, and 3-methyl-2-butenyl acetate, calculated at the HF/6-311G(d,p) level, decreased in the order 2-methyl-2-pentene, 8.97 eV) >3-methyl-2-buten-1-ol, 9.25 eV) >3-methyl-2-butenyl acetate, 9.71 eV, The electron-withdrawing substituents reduce both the electron density of the C=C double bond and the π(O=C) HOMO energy, resulting in a decrease in the reactivity of the olefin with electrophilic oxidants. We carried out the competitive epoxidation of 2-methyl-2-pentene, 3-methyl-2-buten-1-ol, and 3-methyl-2-butenyl acetate to confirm the template effect of the present epoxidation. The reactivity decreased in the order 3-methyl-2-buten-1-ol (2.5)>2-methyl-2-pentene (1.0)>3-methyl-2-butenyl acetate (0.2, This order is not consistent with that of the π(O=C) HOMO energies, showing that the template effect reflects the reactivity of these olefins. The template effect was also observed for the epoxidati
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The π(C=C) HOMO energies of 2-methyl-2-pentene, 3-methyl-2-buten-1-ol, and 3-methyl-2-butenyl acetate, calculated at the HF/6-311G(d,p) level, decreased in the order 2-methyl-2-pentene (-8.97 eV) >3-methyl-2-buten-1-ol (-9.25 eV) >3-methyl-2-butenyl acetate (-9.71 eV). The electron-withdrawing substituents reduce both the electron density of the C=C double bond and the π(O=C) HOMO energy, resulting in a decrease in the reactivity of the olefin with electrophilic oxidants. We carried out the competitive epoxidation of 2-methyl-2-pentene, 3-methyl-2-buten-1-ol, and 3-methyl-2-butenyl acetate to confirm the template effect of the present epoxidation. The reactivity decreased in the order 3-methyl-2-buten-1-ol (2.5)>2-methyl-2-pentene (1.0)>3-methyl-2-butenyl acetate (0.2). This order is not consistent with that of the π(O=C) HOMO energies, showing that the template effect reflects the reactivity of these olefins. The template effect was also observed for the epoxidation of geraniol and geranyl acetate.
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The Xso value of I was lower than or comparable to those reported for stoichiometric reagents such as dimethyldioxirane (0.07, ref, 22a, peracetic acid (0.16, ref, 22b, m-CPBA (0.13, ref, 22b, and HMPT-MoO(O2)2 (0.16, ref, 22c, and for H2O2-based catalytic oxidations such as H 2O2/HClO4 (0.05, ref, 22a, Ti-β (0.07, ref, 22d, Ti-MCM-41 (0.06, ref, 22d, Na2WO 4/C6H5PO3H2/[CH 3(n-C8H17)3N]HSO4 (<0.01, ref, 22e, and CH3ReO3 0.45, ref, 22f
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d) N. J. Cambell, A. C. Dengel, C. J. Edwards, W. P. Griffith, J. Chem. Soc. Dalton Trans. 1989, 1203.
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Cambell, N.J.1
Dengel, A.C.2
Edwards, C.J.3
Griffith, W.P.4
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82
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33846320488
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The reaction of reactive triphenylphosphine (1 mmol) with II (20 μmol) in acetonitrile gave triphenylphosphine oxide (43 μmol), with two equivalents of active oxygen species with respect to II, while the quantitative determination of the active oxygen species by iodometric titration was unsuccessful due to the interference of the tetra(n-butyl)ammonium ions.
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The reaction of reactive triphenylphosphine (1 mmol) with II (20 μmol) in acetonitrile gave triphenylphosphine oxide (43 μmol), with two equivalents of active oxygen species with respect to II, while the quantitative determination of the active oxygen species by iodometric titration was unsuccessful due to the interference of the tetra(n-butyl)ammonium ions.
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83
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33846276561
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Our attempts to obtain crystallographic quality single crystals of [γ-SiW10O32(O2)2] 4- in acetonitrile, acetone, N,N-dimethylformamide, dimethyl sulfoxide, dichloromethane, and 1,2-dichloroethane together with vapor diffusion of poor solvents such as diethyl ether, methanol, n-hexane, n-pentane, and benzene using K, CH3)4N, C2H5)4N, n-C3H 7)4N, n-C4H9) 4N, n-C4H9) 3(PhCH2)N, n-C4H 9)3(CH3)N, Ph(CH 3)3N, Ph4P, K([18]crown-6, K-(dibenzo[18]crown-6, and, iso-C3H7)2NH2, as count
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+ as counterions have been unsuccessful so far. Attempts with the other cations and solvents are in progress.
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84
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33846329109
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29Si NMR signal at δ= -84.1 ppm was observed at 10 min (150 scans) after addition of hydrogen peroxide and the 1!3W NMR spectrum of the solution was the same as that of II (5000 scans, 60 min). Therefore, we estimated that the formation of II was completed within 10 min.
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29Si NMR signal at δ= -84.1 ppm was observed at 10 min (150 scans) after addition of hydrogen peroxide and the 1!3W NMR spectrum of the solution was the same as that of II (5000 scans, 60 min). Therefore, we estimated that the formation of II was completed within 10 min.
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85
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4244166921
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a) S. B. Brown, P. Jones, K. Prudhoe, Inorg. Chim. Acta 1979, 34, 9;
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b) O. Bortolini, F. Di Furia, G. Modena, J. Am. Chem. Soc. 1981, 103, 3924.
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Bortolini, O.1
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Modena, G.3
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87
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33846276922
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It is very difficult to distinguish the bands of peroxo species from those of the polyoxometalate based on the isotopic shifts because the bands related to peroxo species are very weak and overlap with the intense bands of the skeletal vibration of the polyoxometalate
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It is very difficult to distinguish the bands of peroxo species from those of the polyoxometalate based on the isotopic shifts because the bands related to peroxo species are very weak and overlap with the intense bands of the skeletal vibration of the polyoxometalate.
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88
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a) J. Canny, A. Tézé, R. Thouvenot, G. Hervé, Inorg. Chem. 1986, 25, 2119;
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b) A. Tézé, J. Canny, L. Gurban, R. Thouvenot, G. Hervé, Inorg. Chem. 1996, 35, 1001;
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3rd ed, Pergamon, Oxford
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D. D. Perrin, W. L. F. Armarego, Purification of Laboratory Chemicals, 3rd ed., Pergamon, Oxford, 1988.
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W. Adam, D. Golsch, F. C. Görth, Chem. Eur. J. 1996, 2, 255.
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