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Whether the protonolysis takes place via a concerted three-center mechanism or via a prior oxidative addition to the metal,9 an interaction of the proton with the metal is involved, which is expected to be disfavored by the positive charge on the metal when the complex is cationic. Indeed, while in zwitterionic or neutral alkyl derivatives derived from the nucleophilic attack of amines on platinum-olefin complexes the M-C bond is easily cleaved by HCl,10 reversal of the attack was observed in cationic derivatives.5
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13C NMR, 3a-5a were isolated (without separation) from two larger scale reactions, run in the presence of different amounts of the aromatic substrate. Using a slight excess of 1,3-dimethoxybenzene 3a, 4a, and 5a were obtained in 47%, 15%, and 38% molar abundances, respectively. A 10-fold excess of me aromatic substrate favored the monosubstituted products, yielding 3a, 4a, and 5a in 85%, 10%, and 5% molar abundances, respectively.
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13C NMR, 3a-5a were isolated (without separation) from two larger scale reactions, run in the presence of different amounts of the aromatic substrate. Using a slight excess of 1,3-dimethoxybenzene 3a, 4a, and 5a were obtained in 47%, 15%, and 38% molar abundances, respectively. A 10-fold excess of me aromatic substrate favored the monosubstituted products, yielding 3a, 4a, and 5a in 85%, 10%, and 5% molar abundances, respectively.
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4. The solution equilibrated within a few minutes, giving a mixture of 90% 3a, 10% 4a, and only traces of. 5a.
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4. The solution equilibrated within a few minutes, giving a mixture of 90% 3a, 10% 4a, and only traces of. 5a.
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area detector scaling and absorbption correction; Bruker AXS
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