On the Correlation of Hydrogen Bridging Equilibria with Acidity
On the Correlation of Hydrogen Bridging Equilibria with Acidity
复制标题
氢桥平衡与酸度的相关性
DOI：
10.1021/jo01062a024
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发表时间：
1961
影响因子：
3.6
通讯作者：
J. E. Gordon
中科院分区：
文献类型：
--
作者：
J. E. Gordon
关系log Kn Bn.=本文提出用0 log A n HA关联可变酸-参比碱体系HA+ B-*· AH·· B的氢桥平衡与酸度。现有的化学和光谱数据被认为是在很大程度上与此雅阁和类似的表达的质子受体部分的变化。发现类似的表达式适用于桥连离子对A-·· HB+的形成，并且在包含Brpnsted催化定律的情况下，在AH+ B和A-f BH+之间的每个物种（AH···· B，质子转移过渡态，A-·· HB+）的形成可以用log K= xA log K-，ou和适当的系数x来描述。用该模型计算了关联式的数值结果，并与结构、BHB±型络合离子的形成以及质子受体极化率对氢桥稳定性的影响相联系.氢桥强度AH··· B与质子供体和受体部分的酸碱性之间的关系不是新概念;事实上，它在文献中找到了共同的定性就业。1.这一概括的基础和范围：
The relationship log K „Bn.= 0 log A „HA is proposed for correlationof hydrogen bridging equilibria with acidity in the system variable acid-reference base: HA+ B-*· AH··· B. The available chemical and spectroscopic data are found to be largely in accord with this and the analogous expression for variation of the proton acceptor moiety. Analogous expressions are found applicable to formation of the bridged ion pair, A-·· HB+, and on inclusion of the Brpnsted catalysis law, the formation of each of the species (AH··· B, proton transfer transition state, A-·· HB+) intermediate between AH+ B and A-f BH+ can be described by log K= xA log K-, ou with suitable coefficient x. Numerical results of the correlations are com-pared and related to structure usingthis model, as are the formation of complex ions of thetype BHB±and the influence of proton acceptor polarizability on hydrogen bridge stability.The concept of a relationship between the strength of a hydrogen bridge, AH··· B, and the acidity and basicity of the proton donor and accep-tor moieties involved is not a new one; indeed, it finds common qualitative employment in the literature. 1 The basis and scope of this generaliza-