Research on soluble metal sulfides: from polysulfido complexes to functional models for the hydrogenases.
Research on soluble metal sulfides: from polysulfido complexes to functional models for the hydrogenases.
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DOI：
10.1021/ic0343760
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发表时间：
2004-01
影响因子：
4.6
通讯作者：
T. Rauchfuss
中科院分区：
文献类型：
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作者：
T. Rauchfuss
综述了该实验室的研究成果，着重介绍了金属硫化物的合成。描述了四个主题。持续的研究利用多硫化物络合物的放热脱硫作为产生新的簇和环的手段。以这种方式制备的说明性无机环包括1，5-[L（2）M]（2）（S（3））（2）和1，4-[L（2）M]（2）（S（2））（2），其中L（2）M = CpRu（PPh（3））和Cp（2）Ti。在这个项目中制备的新簇合物包括立方烷[（C（5）R（5））MS]（4）（M = Ti，V，Ru，Ir）。相关的氧化还原研究发现了移动的金属-金属键的现象，如[Cp（4）Ir（4）S（4）]（2+）所示，其中局部的Ir-Ir键在簇合物的六个Ir-Ir边缘上迁移。其他脱硫实验导致从[IrS（16）]（3）（-）制备反应性物种Ir（II）（2）S（2）（PPh（3））（4）和合成二茂铁的第一高聚合物[（RC（5）H（3）S）（2）Fe]（n）（n约500）。第二个主题揭示了供体溶剂对金属与硫反应的有用作用。发现吡啶通过Cu（4）（S（5））（2）L（4）的中介作用促进了Cu向晶态CuS的低温转化。相关的合成方法导致了一系列胺稳定的多硫化锌，例如ZnS（6）（tmeda），一种有效的硫转移剂。第三个主题探讨了四硫代甲酸盐的有机和有机金属化学。OsO（4）的硫代类似物ReS（4）（-）被证明对不饱和有机底物如烯烃、炔、腈和异腈具有广泛的反应性。最后，仍然新兴的主题集中在生物有机金属反应中心的功能和结构模型的准备。对纯铁氢化酶模型的研究始于高还原性物种[Fe（2）（SR）（2）（CN）（2）（CO）（4）]（2）（-）的合成，其中（SR）（2）还包括提议的氮杂二硫醇辅因子HN（CH（2）S（-））（2）。通过对氰化物取代反应的系统研究，得到了[HFe（2）（SR）（2）（CN）（CO）（4）（PMe（3））]，它能有效地催化质子还原为H（2）。氢化酶的工作扩展到包括乙酰辅酶A合酶的建模，导致制备含有结合CO底物的混合价Ni（2）模型。
Results from this laboratory are surveyed, emphasizing the synthesis of metal sulfides. Four themes are described. Continuing studies exploit the exothermic desulfurization of polysulfido complexes as a means to generate new clusters and rings. Illustrative inorganic rings prepared in this way include 1,5-[L(2)M](2)(S(3))(2) and 1,4-[L(2)M](2)(S(2))(2), where L(2)M = CpRu(PPh(3)) and Cp(2)Ti. Fundamentally new clusters prepared in this project included the cubanes [(C(5)R(5))MS](4) for M = Ti, V, Ru, Ir. Associated redox studies led to the discovery of the phenomenon of mobile metal-metal bonds, as manifested in [Cp(4)Ir(4)S(4)](2+) wherein the localized Ir-Ir bond migrates over the six Ir- - -Ir edges of the cluster. Other desulfurization experiments led to the preparation of the reactive species Ir(II)(2)S(2)(PPh(3))(4) from [IrS(16)](3)(-) and the synthesis of the first high polymers of ferrocene, [(RC(5)H(3)S)(2)Fe](n) (n approximately 500). A second theme uncovered the useful role of donor solvents on the reaction of metals with sulfur. It was found that pyridine accelerates the low temperature conversion of Cu to crystalline CuS via the intermediacy of the cluster Cu(4)(S(5))(2)L(4). Related synthetic methodology led to a family of amine-stabilized zinc polysulfides, e.g. ZnS(6)(tmeda), an efficient sulfur-transfer agent. A third theme explored the organic and organometallic chemistry of the tetrathiometalates. The sulfido analogue of OsO(4), ReS(4)(-) was shown to be broadly reactive toward unsaturated organic substrates such as alkenes, alkynes, nitriles, and isocyanides. The final and still emerging theme focuses on the preparation of functional and structural models for bio-organometallic reaction centers. Studies on models for the Fe-only hydrogenases began with the synthesis of the highly reducing species [Fe(2)(SR)(2)(CN)(2)(CO)(4)](2)(-) where (SR)(2) also includes the proposed azadithiolate cofactor HN(CH(2)S(-))(2). Systematic studies on the cyanide substitution process led to the preparation of [HFe(2)(SR)(2)(CN)(CO)(4)(PMe(3))], which efficiently catalyzes the reduction of protons to H(2). Work on the hydrogenases was expanded to include modeling of acetyl Co-A synthase, leading to the preparation of mixed valence Ni(2) models containing bound CO substrate.