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Refer to the experimental and Supporting Information sections for further details.
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4043058163
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note
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2OTf to produce product would exhibit a rate law inconsistent with the kinetic data (zero order in styrene concentration would be predicted). For more details and analyses of other less-likely mechanisms refer to the Supporting Information.
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105
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4043060973
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note
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1H NMR spectrum of cyclohexene in the presence of silylsilver complex 8 (relative to cyclohexene without silver) did not provide evidence for the coordination of cyclohexene to silver.
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108
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4043136069
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note
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2(Cl).
-
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111
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4043063797
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note
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1H} NMR spectrum sharpened, and the area of the doublet at 6.23 ppm was noticeably smaller. Examination of the NMR tube, however, revealed the formation of extensive precipitation. Further analysis at this (or lower) temperatures was hampered by the insolubility of the intermediates.
-
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112
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4043093670
-
-
note
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29Si NMR spectrum, the smaller broad singlet at δ 4.52 could either be another product that does not contain silicon or evidence of the formation of an oligomeric silicon phospine compound.
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113
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4043122014
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note
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2SiOTf IR spectra.
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114
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0000877315
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While the isolation of any distinct products was not possible, no spectroscopic evidence for the formation of any Si-H products was observed. For references on various oligomeric silicon products resulting from the decomposition of silylenes refer to: (a) Masamune, S.; Murakami, S.; Tobita, H. Organometallics 1983, 2, 1464-1466.
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Stepwise reactions that involve charged intermediates, such as the hydration and bromination of styrene, are typified by large negative p values. For example: hydration p = -4 (by Schubert, W. M.; Lamm, B.; Keefe, J. R. J. Am. Chem. Soc. 1964, 86, 4727-4729) and bromination p = -4.3 (by Dubois, J. E.; Schwarcz, A. Tetrahedron Lett. 1964, 5, 2167-2173).
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Stepwise reactions that involve charged intermediates, such as the hydration and bromination of styrene, are typified by large negative p values. For example: hydration p = -4 (by Schubert, W. M.; Lamm, B.; Keefe, J. R. J. Am. Chem. Soc. 1964, 86, 4727-4729) and bromination p = -4.3 (by Dubois, J. E.; Schwarcz, A. Tetrahedron Lett. 1964, 5, 2167-2173).
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4043130461
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The shielding or deshielding of vinylic protons (Δδ ppm) between an alkene and a metal-alkene complex was used to generalize the amount of π electron density present on the alkene moiety.
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0001376211
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Electron-rich 2,2′-bipyridine ancillary ligands on copper(I) alkene complexes augmented the electron density present on the bound alkene (relative to free alkene) through increased π back-donation in the copper(I)-ethylene bonding. See: Munakata, M.; Kitagawa, S.; Kosome, S.; Asahara, A. Inorg. Chem. 1986, 25, 2622-2627.
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nOTf.
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4043161546
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Since a limited temperature range (40 °C) was used to determine the activation parameters, caution should be used in drawing firm conclusions from them.
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136
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0001167209
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The uncertainties in the activation parameters were calculated from the error propagation formulas derived by Girolami and Binsch. See: (a) Morse, P. M.; Spencer, M. D.; Wilson, S. R.; Girolami, G. S. Organometallics 1994, 13, 1646-1655.
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