Relative Kinetic Basicities of Organogold Compounds
Relative Kinetic Basicities of Organogold Compounds
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DOI：
10.1021/om901101f
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发表时间：
2010-04-12
期刊：
影响因子：
2.8
通讯作者：
Blum, Suzanne A.
中科院分区：
文献类型：
--
作者：
Roth, Katrina E.;Blum, Suzanne A.
通过竞争性原脱气实验检查了一系列不同取代和杂化的中性有机金化合物的相对动力学碱度，结果发现跨度为 2.2 个数量级。探讨了吸电子和供电子取代基对烯基金和芳基金化合物的原脱气速率的影响。酸抗衡离子效应表明在原脱金属化之前存在金介导的底物预平衡，杂交效应和与 rho(+) = -0.41 的 Hammett 相关性表明 C-C pi 系统参与乙烯基金、炔基金和芳基金配合物的原脱金属。
The relative kinetic basicities of a series of differentially substituted and hybridized neutral organogold compounds were examined through competitive protodeauration experiments and were found to span 2.2 orders of magnitude. The effect of electron-withdrawing and electron-donating substituents on the rate of protodeauration of alkenylgold and arylgold compounds was explored. An acid counterion effect indicated the presence of a gold-mediated substrate preequilibrium before protodemetalation, and hybridization effects and a Hammett correlation with rho(+) = -0.41 indicated the involvement of the C-C pi system in the protodeauration of vinylgold, alkynylgold, and arylgold complexes.