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Using Second Coordination Sphere Interactions of Rhenium(I) Complexes to Promote

利用铼(I)配合物的第二配位层相互作用来促进

基本信息

批准号：
8311167
负责人：
Loi Hung Do
金额：
$ 4.92万
依托单位：
CALIFORNIA INSTITUTE OF TECHNOLOGY
依托单位国家：
美国
项目类别：
财政年份：
2011
资助国家：
美国
起止时间：
2011-08-01 至 2013-07-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/8311167
关键词：
Accounting Acids Adopted Area Binding Biomass Carbon Carrying Capacities Cell Nucleus Characteristics Chemical Industry Chemicals Chemistry Cleaved cell Coal Complex Consumption Coupling Data Deterioration Economics Ecosystem Electronics Electrons Electrostatics Ensure Environment Future Gases Goals Growth Habitats Health Human Human Development Hydrocarbons Hydrogen Hydrogen Bonding Industrialization Investigation Kinetics Knowledge Lead Left Ligands Link Liquid substance Mass Spectrum Analysis Mediating Metals Methodology Methods Molecular NMR Spectroscopy Natural Gas Natural regeneration Petroleum Phosphines Planets Plants Pollution Process Production Quality of life Reaction Reagent Relative (related person)Reliance Research Research Proposals Resources Rhenium Social Welfare Source Staging System Technology Testing Thermodynamics Transition Elements Translating Uncertainty United States Work X-Ray Crystallography catalyst chemical bond design economic value improved infrared spectroscopy interest metal complex novel polymerization scaffold

项目摘要

DESCRIPTION (provided by applicant): Given the limited resources on this planet, it is imperative that chemical industries adopt more sustainable practices to ensure future economic growth as well as to protect the welfare of people and the environment. Our current reliance on petroleum as fuel and organic raw materials is inadequate due to uncertainty in its supply and the enormous amount of pollution associated with its processing. Finding an alternative carbon source requires: 1) identifying a reliable and naturally abundant chemical feedstock, and 2) discovering clean technologies to convert it into value-added products. With regard to these goals, a promising area of research is in the industrial use of synthesis gas (syngas), CO and H2, which can be readily obtained from coal and biomass. Although several large-scale manufacturing plants utilize syngas to produce hydrocarbons and oxygenates, current synthetic methods that rely on Fischer-Tropsch chemistry is non-selective. The additional steps needed to separate syngas products greatly reduce its overall synthetic efficiency. Homogeneous catalysts that mediate C-H and C-C bond forming reactions from syngas may allow selective coupling of CO by circumventing the thermodynamic and kinetic restrictions that have traditionally hindered such reactivity. Bercaw and coworkers have demonstrated that some of the key reaction steps in a possible catalytic cycle involving CO can be achieved using phosphine-supported metal carbonyl complexes and hydride donors obtained from heterolytic cleavage of H2. Although these studies led to successful reductive coupling of two CO molecules, the resulting product was too stable to be regenerated for a viable catalytic reaction. This proposal describes the design of a novel rhenium carbonyl platform for reductive coupling of CO using syngas as the exclusive source of carbon, hydrogen, and electrons. A multi-functional ligand provides an opportunity to explore the influence of second coordination sphere interactions, such as hydrogen bonding, Lewis acid activation, and electrostatic attraction, on the reactivity of metal carbonyl species toward hydride donors. The primary goal of this work is to determine what factors promote C-H and C-C bond forming processes, knowledge of which will be used to design catalytic systems for selective transformation of syngas into higher-carbon containing materials.

描述（由申请人提供）：鉴于地球上的资源有限，化学工业必须采取更可持续的做法，以确保未来的经济增长以及保护人类和环境的福祉。由于石油供应的不确定性以及与石油加工相关的大量污染，我们目前对石油作为燃料和有机原材料的依赖是不够的。寻找替代碳源需要：1）确定可靠且天然丰富的化学原料，2）发现清洁技术将其转化为增值产品。就这些目标而言，一个有前景的研究领域是合成气（syngas）、CO和H2的工业使用，它们可以很容易地从煤炭和生物质中获得。尽管一些大型制造工厂利用合成气来生产碳氢化合物和含氧化合物，但目前依赖费托化学的合成方法是非选择性的。分离合成气产品所需的额外步骤大大降低了其整体合成效率。介导合成气中C-H和C-C键形成反应的均相催化剂可以通过规避传统上阻碍此类反应性的热力学和动力学限制来选择性偶联CO。 Bercaw 和他的同事已经证明，可能涉及 CO 的催化循环中的一些关键反应步骤可以使用膦负载的金属羰基络合物和从 H2 异裂获得的氢化物供体来实现。尽管这些研究成功地实现了两个 CO 分子的还原偶联，但所得产物太稳定，无法再生以进行可行的催化反应。该提案描述了一种新型铼羰基平台的设计，用于使用合成气作为碳、氢和电子的唯一来源来还原耦合 CO。多功能配体提供了探索第二配位层相互作用（例如氢键、路易斯酸活化和静电吸引）对金属羰基物质对氢化物供体的反应性的影响的机会。这项工作的主要目标是确定哪些因素促进 C-H 和 C-C 键形成过程，这些知识将用于设计催化系统，以选择性地将合成气转化为含碳较高的材料。