Use of Kinetic Isotope Effects in Mechanism Studies. 5.1 Isotope Effects and Element Effects Associated with Hydron-Transfer Steps during Alkoxide-Promoted …

HF Koch, G Lodder, JG Koch, DJ Bogdan…

文献索引：Koch, Heinz F.; Lodder, Gerrit; Koch, Judith G.; Bogdan, David J.; Brown, Geoffrey H.; Carlson, Carrie A.; Dean, Amy B.; Hage, Ronald; Han, Patrick; Hopman, Johan C. P.; James, Lisa A.; Knape, Petra M.; Roos, Eric C.; Sardina, Melissa L.; Sawyer, Rachael A.; Scott, Barbara O.; Testa III, Charles A.; Wickham, Steven D. Journal of the American Chemical Society, 1997 , vol. 119, # 42 p. 9965 - 9974

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被引用次数: 14

摘要

The Arrhenius behavior of the primary kinetic isotope effect,(k H/k D) Obs and (k H/k T) Obs, associated with the methanolic sodium methoxide-promoted dehydrohalogenations of m- ClC6H4CiHClCH2Cl (I), m-CF3C6H4CiHClCH2Cl (II) and p-CF3C6H4CiHClCH2F (III) has been used to calculate the internal-return parameters, a= k-1/, in a two-step mechanism featuring a hydrogen-bonded carbanion. This carbanion partitions between returning the ...