Organometallic Cluster Chemistry: Higher Nuclearity Derivatives

有机金属簇化学：高核衍生物

• 批准号: 9414217
• 负责人: John Shapley
• 金额: $ 37.48万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-12-01 至 1997-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9414217&HistoricalAwards=false
• 关键词: Organometallic; Cluster; Chemistry; Higher; Nuclearity

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.

9414217 Shapley University of Ill. Urbana-Champaign Dr.沙普利，伊利诺伊大学。Urbana-Champaign由化学部的无机，生物无机和有机化学计划支持，以开发含有6至12个金属原子的中间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）与碳基七铼簇有关并含有亚甲基部分的化合物;（2）采用独特结构的十钌簇体系的烃配体衍生物，该独特结构显然可以“重构”以结合烃基;（3）其中七铼簇单元在结合金属络合物片段时模拟常见的配体，但在金属顶点处产生增强的反应性的化合物;和（4）一氧化碳在六钌骨架上的反硝化过程，该反应是表面Boudouard反应的直接分子类似物，并且对于引发费-托烃合成过程可能是重要的。 金属在许多重要的工业化学过程（包括石油精炼）中用作催化剂。然而，金属表面如何能够进行和促进化学反应的细节尚未清楚地了解。该项目的重点是一系列含有6至12个金属原子的化合物。这些复合物足够小，可以详细研究它们与其他物种相互作用的细节，但又足够大，可以模拟金属表面。选择用于调查的物种代表特别合适的模型的粗糙的金属表面上的网站是最活跃的C-C，C-N，和C-O键断裂。除了提供对金属介导的化学反应的基本理解之外，还将制备新类别的有机金属簇合物，其本身可能显示催化性能。