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

• 批准号: 8198732
• 负责人: Loi Hung Do
• 金额: $ 4.63万
• 依托单位: CALIFORNIA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-08-01 至 2014-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8198732
• 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

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. PUBLIC HEALTH RELEVANCE: If immediate actions are not taken to remedy the harmful effects of industrialization on our ecosystems, further damage to our habitat will also threaten human health. One positive step toward a more sustainable future is to develop greener technologies to utilize earth abundant resources for fuel and material goods. This work aims to discover new synthetic methods to convert synthesis gas, which can be readily obtained from coal and biomass, into more valuable commodities with a low environmental footprint.

描述（由申请人提供）：鉴于该星球上的资源有限，化学工业必须采用更可持续的实践来确保未来的经济增长以及保护人们和环境的福利。我们目前对石油作为燃料和有机原材料的依赖不足，因为其供应不确定性以及与其加工相关的巨大污染。寻找替代碳源需要：1）确定可靠且自然丰富的化学原料，2）发现清洁技术以将其转换为增值产品。关于这些目标，有希望的研究领域是合成气体（Syngas），CO和H2的工业使用，可以很容易地从煤炭和生物量中获得。尽管几家大型制造工厂利用合成剂来产生碳氢化合物和氧化剂，但依赖Fischer-Tropsch化学的当前合成方法是非选择性的。分离Syngas产品所需的其他步骤大大降低了其整体合成效率。 介导C-H和C-C键反应的同质催化剂可以通过绕过传统上阻碍这种反应性的热力学和动力学限制来选择性耦合CO。 Bercaw及其同事表明，可以使用磷酸支持的金属羰基复合物和从H2的杂溶解裂解获得的催化循环中的某些关键反应步骤。尽管这些研究导致了两个CO分子的成功还原性耦合，但所得的产物太稳定而无法再生以产生可行的催化反应。 该建议描述了一种新型的rhenium羰基平台的设计，用于使用Syngas作为碳，氢和电子的专有来源，以还原CO的还原耦合。多功能配体提供了探索第二配位球相互作用的影响，例如氢键，刘易斯酸激活和静电吸引力对金属羰基物种对氢化物供体的反应性的影响。这项工作的主要目标是确定哪些因素促进了C-H和C-C键形成过程，其知识将用于设计催化系统，以选择将Syngas转化为含有较高碳的材料的催化系统。 公共卫生相关性：如果不立即采取行动来纠正工业化对我们生态系统的有害影响，则对我们栖息地的进一步损害也会威胁到人类健康。朝着更可持续的未来迈出的积极一步是开发更绿色的技术，以利用地球丰富的资源来燃料和物质商品。这项工作旨在发现新的合成方法转化合成气，可以很容易地从煤炭和生物质中获得的合成气体，转化为具有较低环境足迹的更有价值的商品。