Organometallic Cluster Chemistry: Higher Nuclearity Derivatives

沙普利大学9414217号伊利诺伊州。厄巴纳-香槟大学约翰·R·沙普利博士伊利诺伊州。Urbana-Champaign，由化学部无机化学、生物无机化学和金属有机化学计划支持，开发含有6至12个金属原子的中等尺寸过渡金属羰基簇合物的有机金属化学。要研究的具体体系包括：(1)与碳基七氢稀土簇合物有关并含有亚甲基部分的化合物；(2)采用独特结构的十钚簇合物体系的碳氢配体衍生物，该结构显然可以重新构建以结合碳氢基；(3)其中七茂金属簇合物单元模仿普通的环戊二烯配体结合金属络合物片段，但在金属顶点产生增强的反应活性的化合物；和(4)一氧化碳在六钚骨架上歧化的过程，该反应是表面Boudouard反应的直接分子模拟，可能对启动Fischer-Tropsch烃合成过程很重要。金属在许多重要的工业化学过程中用作催化剂，包括提炼石油。然而，关于金属表面如何能够进行和促进化学反应的细节尚不清楚。这个项目的重点是一系列含有6到12个金属原子的化合物。这些复合体足够小，可以非常详细地研究它们与其他物种相互作用的细节，但也足够大，可以模拟金属表面。被选择用于研究的物种代表了特别适合于在粗糙的金属表面上最活跃地破坏C-C、C-N和C-O键的位置的模型。除了提供对金属介导的化学反应的基本了解外，还将制备新类型的有机金属簇合物，它们本身可能具有催化性能。

9414217 Shapley Univ. of Ill. Urbana-Champaign Dr. John R. Shapley, Univ. of Ill. Urbana-Champaign, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to develop the organometallic chemistry of intermediate sized transition metal carbonyl cluster compounds which contain six to twelve metal atoms. The specific systems to be studied include: (1) compounds which are related to a carbido heptarhenium cluster and which contain a methylene moiety; (2) hydrocarbon ligand derivatives of a decaruthenium cluster system which adopts a unique structure that apparently can 'reconstruct' in order to bind a hydrocarbon group; (3) compounds in which a heptarhenium cluster unit mimics the common cyclopentadienyl ligand in binding a metal complex fragment but engenders enhanced reactivity at the metal vertex; and (4) the process of carbon monoxide disproportionation on a hexaruthenium framework, a reaction that is a direct molecular analog of the surface Boudouard reaction and one that may be important for initiating the Fischer-Tropsch hydrocarbon synthesis process. Metals are used as catalysts in a number of important industrial chemical processes including the refining of petroleum. However, the details of how metal surfaces are able to carry out and facilitate chemical reactions is not yet clearly understood. This project focuses on a series of compounds which contain six to twelve metal atoms. These complexes are small enough to permit the details of their interactions with other species to be studied in great detail, but large enough to model metal surfaces. The species chosen for investigation represent particularly suitable models for the sites on roughened metal surfaces that are most active in breaking C-C, C-N, and C-O bonds. In addition to providing a basic understanding of metal mediated chemical reactions, new classes of organometallic cluster compounds, which themselves may show catalytic properties will be prepared.