BINUCLEAR METAL-POLYPYRIDYL MOLYBDENUM OXO-THIOLATES AS MODEL FOR OXOTRANSFERASES

钼作为一种微量元素在人体中的作用是重要的 一个;它存在于“氧代转移酶”的活性位点中。 酶亚硫酸盐氧化酶、黄嘌呤脱氢酶、醛 转移酶作为钼辅因子， 这些酶的运作。 低水平的儿童 起作用的亚硫酸盐氧化酶和黄嘌呤脱氢酶已经被 被发现表现出智力迟钝，神经系统异常， 晶状体移位和身体发育迟缓。 在这个项目中，一系列的合成和表征， 类似化合物，MoS 2-nOn（mu-S）2 Ru（ii）Lx（Lx=2，2 '-联吡啶 （联吡啶）或2，6-双（2 '-吡啶基）吡啶（三联吡啶）+ H2O）将是 执行。 在这一系列化合物中，钼原子将 协调领域类似于提议的主动 黄嘌呤脱氢酶和亚硫酸盐氧化酶的位点， 键合到单电子氧化还原活性钌多吡啶配合物上 通过桥接硫化物基团。 表征方法将 包括电子吸收光谱的研究， 这些络合物的电化学和化学反应性。 的 将研究氧化和还原产物的性质 在光吸收和EPR中通过原位电解 光谱细胞 长期目标是调查 (a)该系统的反应性范围，以及（B） 共价连接的过渡金属络合物作为 简单的氧化还原水库模型系统。

The role of molybdenum as a trace element in humans is an important one; it is present in the active site in the "oxotransferase" enzymes sulfite oxidase, xanthine dehydrogenase, aldehyde transferase as the molybdenum co-factor which is necessary for these enzymes to operate. Children who have low levels of functioning sulfite oxidase and xanthine dehydrogenase have been found to exhibit mental retardation, neurological abnormalities, displaced ocular lenses and retarded physical development. In this project, the synthesis and characterization of a series of analogous compounds, MoS2-nOn(mu-S)2Ru(ii)Lx(Lx=2, 2'-bipyridine (bipy) or 2,6-bis(2'-pyridyl)pyridine (terpy) + H2O) will be performed. In this series of compounds, the molybdenum atom will have coordination spheres similar to those proposed for the active sites of xanthine dehydrogenase and sulfite oxidase and will be bonded to one electron redox active ruthenium polypyridyl complexes by bridging sulfide groups. Methods of characterization will include investigations of the electronic absorption spectrum, electrochemistry and chemical reactivity of these complexes. The nature of the oxidation and reduction products will be investigated through in situ electrolysis in optical absorption and EPR spectroscopic cells. The long term objectives are to investigate (a) the scope of the reactivity of such systems and (b) the viability of covalently attached transition metal complexes as simple redox reservoirs in model systems.