BIOLOGICALLY RELATED IRON-SULFUR CHEMISTRY

拟议研究的广泛目标是阐明 形成途径，结构，电子和反应性 性质和生理功能的含金属 铁硫蛋白和酶的配位位点。 该方法被 的活性位点的合成类似物的方法， 金属生物分子，其中低分子量位点表示是 制备并在小分子水平上仔细检查其性能， 详细 本论文主要研究了以下几个方面的问题：（1）环己基苯甲酸的合成 多硫醇配体设计用于稳定某些核心结构， 氧化水平。 [Fe-mS-n]z的合成与表征 [Fe 2S 2]1+和[Fe 4S 4]3+团簇，以确定详细结构 以及电子离域性质;（3）合成与表征 的三核簇[Fe 3S 4]1+，O的主要意图， 为蛋白质Fe 3S 4簇提供结构证明， 簇重构反应;（4）双立方烷簇的合成 用于评估分子内电子相互作用;（5） Fe_4S_4簇合物合成与表征 在一个配体位点官能化;（6）反应顺序的说明 导致形成还原的铁氧还蛋白类似物 [Fe_4S_4（SR）_4]~（3-），（7）内禀核结构变化的定义 伴随着生物普遍的[Fe 4S 4]2+，1+电子转移 反应;（8）开发的结构和功能模型的 亚硫酸盐和亚硝酸盐还原酶的活性位点，包括 通过合成减少的底物中间体，（9）合成和 含[Fe_2S]~（3+）、~（4+）、~（5+）桥单元配合物的表征 与硫代血红素类似;（10）继续发展 金属硫醇盐化学，重点是几何和电子 [M（SR）4]1-，2-和[M2（SR）6]2-物种的结构和反应性。

The broad objective of the proposed research is the elucidation of the pathways of formation, the structural, electronic, and reactivity properties, and the physiological functions of the metal-containing coordination sites of iron-sulfur proteins and enzymes. The methodology is that of the synthetic analogue approach to the active sites of metallobiomolecules, whereby low molecular weight site representations are prepared and their properties scrutinized at the small molecule level of detail. These problems will be undertaken: (1) synthesis of cyclic polythiol ligands designed to stabilize certain core structures and oxidation levels. [Fe-mS-n]z, (2) synthesis and characterization of [Fe2S2]1+ and [Fe4S4]3+ clusters in order to determine detailed structures and electron delocalization properties; (3) synthesis and characterization of the trinuclear clusters [Fe3S4]1+,O with the main intentions of providing a structure proof for protein Fe3S4 clusters and examining cluster reconstitution reactions, (4) synthesis of double-cubane clusters for the purpose of assessing intramolecular electronic interactions; (5) synthesis and characterization of Fe4S4 clusters specifically functionalized at one ligand site; (6) elucidation of the reaction sequence leading to the formation of the reduced ferredoxin analogues [Fe4S4(SR)4]3-, (7) definition of the intrinsic core structural change accompanying the biologically pervasive [Fe4S4]2+,1+ electron transfer reaction; (8) development of a structural and functional model of the active sites of sulfite and nitrite reductase, including examination of reduced substrate intermediates by synthesis, (9) synthesis and characterization of complexes containing the [Fe2S]3+,4+,5+ bridge unit similar to that in sulfidohemerythrin; (10) continued development of metal-thiolate chemistry, with emphasis on the geometrical and electronic structures and reactivities of [M(SR)4]1-,2- and [M2(SR)6]2- species.