SIMULATION OF FREE-ENERGY RELATIONSHIPS AND DYNAMICS OF SN2 REACTIONS IN AQUEOUS-SOLUTION
SIMULATION OF FREE-ENERGY RELATIONSHIPS AND DYNAMICS OF SN2 REACTIONS IN AQUEOUS-SOLUTION
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DOI：
10.1021/ja00224a011
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发表时间：
1988-08-03
影响因子：
15
通讯作者：
WARSHEL, A
中科院分区：
文献类型：
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作者：
HWANG, JK;KING, G;WARSHEL, A
概述镉、铅和T1汞齐电极在氯化或芳香族碳氢溶剂等非配位介质中的电化学氧化产生一种高度活化的金属离子，它与通常被认为是非配位配体的[C104]~和[BF4]阴离子强烈络合。因此，如果配体在电极表面的反应速度快于沉淀动力学，那么就有可能获得一条通向以前未知的络合物的途径。在二氯甲烷中可溶的[Cd(C104)4]1 2345-、[Cd(BF4)3]-、[Pb(C104)3]-、Pb(BF4)2、T1(C104)和T1(BF4)络合物的鉴定是新络合物的一个例子，非溶剂化Cd(BF4)2的简单电化学合成也是一个例子。我们感谢澳大利亚研究资助计划(AMB)、迪肯大学研究委员会提供的博士后研究奖学金(SRE)以及英联邦教育部提供的研究生奖学金(AFH)。
Summary The electrochemical oxidationof Cd, Pb, and T1 mercury amalgam electrodes in noncoordinating mediasuch as chlorinated or aromatic hydrocarbonsolvents generates a highly activated form of the metal ion, which is strongly complexed by both [C104]~ and [BF4]“, anions that are normally regarded as noncoordinating ligands. Thus, if ligands can react at the electrode surface faster than the kinetics of precipitation, then a pathway to previously unknown complexes is available. The identificationof soluble [Cd (C104) 4] 1 2 345-,[Cd (BF4) 3]-,[Pb (C104) 3]-, Pb (BF4) 2, T1 (C104), and T1 (BF4) complexes in dichloromethane is an example of new complexes as is the facile electrochemical synthesis of nonsolvated Cd (BF4) 2.Acknowledgment. We thank the Australian Research Grants Scheme for financial support (AMB), Deakin University Re-search Committee for the provision of a postdoctoral research fellowship (SRE), and the Commonwealth Education Depart-ment for a postgraduate scholarship (AFH).