KINETICS AND OXIDATION MECHANISMS OF NONMETALLICS BY TRANSITION METAL COMPLEXES

涉及软中心的电子转移反应的机理 因为硫磺很耐人寻味，因为有大量的化合物 含有生物上重要的巯基和二硫基。其中之一 这种类型就是用于甲状腺的咪唑-2-硫酮 过氧化物酶催化的甲状腺球蛋白的碘化。另一个例子是 2-硫氧嘧啶衍生物在甲亢治疗中的应用。 由于在体内可能与硫基自由基有关 生物化学过程，很明显，大自然和 各种氧化剂的氧化反应机理必须 有助于更好地理解硫氢基的作用 和二硫化物的药效。 在目前的提案中，我们计划研究动力学和 上述单电子和多电子氧化还原过程的机理 转移过渡金属络合物作为氧化剂，比较不同的 当配位和配位变化时，反应可能采取的路径 自由能是强加的。所有的过渡金属都将是不寻常的 具有取代惰性的超氧化态 氧化还原化学的控制。 学生参与者将有机会合成， 表征并研究这些络合物的反应动力学。 他们将被教授制备无机络合物的程序以及如何 使用各种乐器。预计他们将全面参与 小组会议和会议报告。

The mechanisms of electron transfer reactions involving soft center such as sulfur is intriguing since there are a multitude of compounds containing biologically important sulfhydryl and disulfide groups. One of such types is the imidazole-2-thione which is used in the thyroid peroxidase-catalyzed iodination of thyroglobulin. Another example is the use of 2-thiouracil derivatives in the treatment of hyperthyroidism. Since thiyl free radicals might be implicated in the above in vivo biochemical processes, it becomes apparent that the nature and the mechanisms of the oxidation reactions with various oxidizing reagents must be understood to permit a better understanding of the role of sulhydryl and disulfide in the efficacy of the medicine. In the present proposal, we plan to investigate the kinetics and mechanisms of the above redox processes with single and multi-electron transfer transition metal complexes as oxidants and compare the different pathways the reactions might have taken when changes in coordination and free energy are imposed. All the transition metals will be of unusual hyper oxidation states with substitution inert property essential for the control of the redox chemistry. Student participants will be given the opportunity to synthesize, characterize, and study the kinetics of reactions of these complexes. They will be taught the procedure to prepare inorganic complexes and how to use various instruments. They are expected to participate fully in group meetings and in conference presentations.