ELECTRON TRANSFER REACTIONS OF AMINO NITROGEN COMPOUNDS

电子转移反应具有基本的生物学重要性， 仍然是最不了解的主要类别的反应机理 类型 最重要的问题被公认为是理解 是什么控制着自我ET的速率，比如中性化合物的速率 与自己的阳离子自由基反应，因为已经证明， 其他ET反应的速率可以定量预测，如果自我- 组分的ET速率是已知的。 人们普遍认为， 有机化合物中的ET主要由以下必要性控制： 溶剂重组达到过渡态，内部 衬底中的几何形状变化仅具有较小的影响。 建议 目前对控制ET率的因素的解释 严重的错误，并为实验提供新的实验数据， 将对这些解释进行测试。 与大多数有机食品相比， 化合物，其自ET以接近扩散控制速率进行， 对于肼类化合物，self-ET对烷基结构敏感， 组，并进行速率常数>10 5比扩散慢 控制 一个特殊的系列肼，倍半双环，已被 已开发的渐进式结构变化，以及 其详细描述了作为温度，溶剂， 将进行立体化学研究。 酰化的羟胺和二酰肼提供式（I）的化合物： 几何重组的中等重要性，这将允许 进一步探索ET速率理论，在分子内和分子间 反应. 这些化合物是测试当前ET理论的理想选择。 立体电子效应对烷基化和氧化脱氢的影响 还将研究氨基氮化合物。

Electron transfer reactions are of fundamental biological importance but remain the least understood of the major classes of reaction mechanistic types. The most important problem is well accepted to be understanding what controls the rate of self-ET, such as that for a neutral compound reacting with its own cation radical, because it has been shown that rates for other ET reactions can be quantitatively predicted if the self- ET rates of the components are known. It has been widely believed that ET in organic compounds is principally controlled by the necessity for solvent reorganization to reach the transition state, and that internal geometry change in the substrate has only minor effects. It is suggested that interpretation of the factors controlling ET rate is currently seriously in error, and experiments to provide new experimental data to test these interpretations will be done. In contrast to most organic compounds, for which self-ET proceeds at near diffusion controlled rates, for hydrazines self-ET has is sensitive to he structure of the alkyl groups, and proceeds with rate constants >10 5 slower than diffusion control. A special series of hydrazines, sesquibicyclics, has been developed for which graduated structural changes are available, and for which detailed rate measurements as a function of temperature, solvent, and counterion will be carried out, as well as stereochemical studies. Acylated hydroxylamines and diacylhydrazines provide compounds of intermediate importance of geometry reorganization, which will allow further probing of ET rate theories, in both intra- and intermolecular reactions. These compounds are ideal for testing current theories of ET. Stereoelectronic effects on alkylation and oxidative dehydrogenation of amino nitrogen compounds will also be investigated.