KINETICS AND OXIDATION MECHANISMS OF NONMETALLICS BY TRANSITION METAL COMPLEXES

过渡金属配合物对非金属的动力学和氧化机制

• 批准号: 6107377
• 负责人: HENRY N PO
• 金额: --
• 依托单位: CALIFORNIA STATE UNIVERSITY LONG BEACH
• 依托单位国家: 美国
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-08-01 至 1999-01-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6107377
• 关键词: amines; chemical kinetics; chemical synthesis; electrochemistry; electron transport; heavy metals; metal complex; oxidation reduction reaction; oxidizing agents; silver; stop flow technique; thermodynamics; thiols; ultraviolet spectrometry

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.

对涉及软中心的电子转移反应的机理进行了探讨， 因为硫是有趣的，因为有许多化合物 含有生物学上重要的巯基和二硫基。 之一 这种类型是咪唑-2-酮，用于甲状腺 甲状腺球蛋白的过氧化物酶催化碘化。 另一个例子是 2-硫氧嘧啶衍生物在治疗甲状腺机能亢进中的用途。 由于在体内，巯基自由基可能参与上述过程， 生物化学过程中，很明显，自然和 与各种氧化剂的氧化反应的机理必须 可以理解为允许更好地理解巯基的作用 和二硫化物。 在本提案中，我们计划研究动力学， 单电子和多电子氧化还原过程的机理 转移过渡金属配合物作为氧化剂，并比较不同的 反应可能采取的途径时，协调和 自由能是强加的。 所有的过渡金属将是不寻常的 具有取代惰性性质的超氧化态， 氧化还原化学的控制。 学生参与者将有机会综合， 表征，并研究这些配合物的反应动力学。 他们将被教导的程序，以制备无机复合物，以及如何 使用各种工具。 预计他们将充分参与 小组会议和会议演示。