METALLO-SULFUR COMPLEXES AS MODELS FOR ELECTRON TRANSFER PROTEINS

金属二硫代络合物和金属二硫化物的化学 配合物将作为金属硫醇盐的模型体系进行研究 电子传递蛋白，如普遍存在的铁硫蛋白， proteins. 据推测，这些金属蛋白可以获得 通过形成部分S.S键的额外还原能力 通过两个相邻的金属结合的硫醇盐的相互作用。 这一假设的证据来自于一些例子， 金属-硫醇盐络合物，其中S.S分离相当大， 小于预测的非结合的最近邻接触 硫原子 将合成金属硫络合物，其中 二硫醇盐/二硫化物偶联是可逆的。 二硫 将用高价金属离子制备络合物， 将用低价金属离子制备二硫化物络合物。 硫醇盐络合物的氧化和硫醇盐络合物的还原 二硫键复合物将进行研究，以提供进一步的 二硫代硫酸盐/二硫键偶作为来源的证据 电子转移蛋白质的还原能力增加。

The chemistry of metal-dithiolate complexes and metal disulfide complexes will be studied as model systems for metallo-thiolate electron transport proteins such as the ubiquitous iron-sulfur proteins. It is proposed that these metalloproteins can obtain additional reducing power by the formation partial S.S bonds through interaction of two adjacent metal-bound thiolates. Evidence for this hypothesis comes from a number of examples of metal-thiolate complexes where the S.S separations are considerably smaller than the predicted nearest neighbor contact of non-bonded sulfur atoms. Metallosulfur complexes will be synthesized where the dithiolate/disulfide couple is reversible. Dithiolate complexes will be prepared with high-valent metal ions while disulfide complexes will be prepared with low-valent metal ions. The oxidation of the thiolate complexes and the reduction of the disulfide complexes will be studied in order to provide further evidence for the dithiolate/disulfide couple serving as a source of increased reducing power in electron transfer proteins.