ELECTRON TRANSFER REACTIONS OF AMINO NITROGEN COMPOUNDS

电子转移反应具有基本的生物学重要性，但 仍然是反应机理的主要类别中最不被了解的 类型。人们普遍认为最重要的问题是理解 是什么控制着自我ET的速率，比如中性化合物的速率 与它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，如果自身 组件的ET速率是已知的。人们普遍认为， 有机化合物中的ET主要受以下因素的影响 达到过渡状态的溶剂重组，以及内部 衬底中的几何变化只有很小的影响。有建议说 对控制ET率的因素的解释目前是 严重错误，实验提供了新的实验数据 测试这些解释将会完成。与大多数有机食品不同 化合物，其自我ET以接近扩散控制的速度进行， 对于肼类化合物，自组氨酸对烷基的结构很敏感 分组，并以比扩散慢105的速率常数继续进行 控制力。一种特殊的联氨系列，倍半环，已经被 为其提供渐进式结构变化的开发，以及为 其详细的速率测量作为温度、溶剂、 和反离子，以及立体化学研究。 酰化羟胺和二酰肼提供以下化合物 几何重组的中等重要性，这将允许 分子内和分子间ET速率理论的进一步探讨 反应。这些化合物是检验当前外星人理论的理想选择。 烷基化和氧化脱氢反应的立体电子效应 氨基氮化合物也将被调查。

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.