Mechanisms of Transition Metal Catalyzed Reactions in Hydrocarbons

过渡金属催化烃类反应的机理

• 批准号: 1212767
• 负责人: Robert Grubbs
• 金额: $ 61.5万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-08-01 至 2016-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1212767&HistoricalAwards=false
• 关键词: Mechanisms; Transition; Metal; Catalyzed; Reactions

The Chemical Structure, Dynamics and Mechanism Program supports Professor Robert H. Grubbs of the California Institute of Technology for the development of a family of catalysts for the inter-conversion of olefins by the olefin metathesis reaction. NSF support for this work began decades ago with the determination of the basic mechanism of the reaction. Today these catalysts find themselves widely used in academic research and in significant commercial applications. These advances include the discovery of new inorganic complexes that show improved activity or selectivity. A number of limitations that remain: the present grant focuses on new catalyst systems, a better understanding of regiochemical and stereochemical issues and the observed low efficiency of the catalysts in the presence of ethylene. These complexes operate by a novel mechanism, and new families of ligands and complexes will be constructed for these catalytic transformations as the mechanism is better understood. The ruthenium complexes that induce the metathesis of acyclic olefins can also be used for the ring opening polymerization (ROMP) of cyclic olefins. Numerous well-defined polymers have been produced using these complexes as living initiators for the synthesis of block and highly functional polymers. A special class of polymers that is of interest for theoretical reasons and may have interesting applications are polymers without ends-cyclic polymers. A set of ruthenium complexes has been prepared that produce cyclic polymers from cyclic monomers. To be able to test standing theories, polymers that are pure cyclics without linear contaminations are required. A method has been developed that should result in pure cyclics with a range of molecular weights. In terms of broader impacts and benefits to society, these catalyst systems are currently being used for an array of successful commercial applications. New pharmaceuticals that require the closure of a large ring using these catalysts are being developed and are in clinical trials. A bio-refinery is being constructed that utilizes the complexes for the conversion of seed oils into chemicals and fuels. In the production of new materials, polymers that require the NSF catalysts in their production have been used in the automotive market for a number of years. In addition, new polymer composite materials are being produced for the construction of large-scale mechanical devices.

化学结构，动力学和机制计划支持教授罗伯特H。Grubbs的发明，用于开发通过烯烃复分解反应使烯烃相互转化的催化剂族。 NSF对这项工作的支持始于几十年前，当时确定了反应的基本机制。 今天，这些催化剂被广泛用于学术研究和重要的商业应用。 这些进展包括发现了具有更高活性或选择性的新无机复合物。 一些限制仍然存在：目前的赠款侧重于新的催化剂系统，更好地了解区域化学和立体化学问题，以及在乙烯存在下观察到的催化剂效率低。这些配合物通过一种新的机制进行操作，随着对该机制的更好理解，将为这些催化转化构建新的配体和配合物家族。 诱导无环烯烃复分解的钌络合物也可用于环烯烃的开环聚合（ROMP）。 使用这些配合物作为活性引发剂合成嵌段和高功能聚合物已经产生了许多定义明确的聚合物。 一类特殊的聚合物，是感兴趣的理论原因，并可能有令人感兴趣的应用是聚合物没有结束-环状聚合物。 已经制备了一组钌配合物，可以从环状单体产生环状聚合物。 为了能够测试现有的理论，需要没有线性污染的纯环状聚合物。 已经开发了一种方法，该方法应产生具有一定分子量范围的纯环状化合物。 就对社会的更广泛影响和益处而言，这些催化剂系统目前正用于一系列成功的商业应用。 需要使用这些催化剂闭合大环的新药物正在开发中，并处于临床试验中。 正在建造一个生物炼油厂，利用这些复合物将种子油转化为化学品和燃料。 在新材料的生产中，在生产中需要NSF催化剂的聚合物已在汽车市场中使用多年。 此外，正在生产用于建造大型机械装置的新型聚合物复合材料。