Mechanisms of Transition Metal Catalyzed Reactions in Hydrocarbons

化学结构、动力学和机理计划支持加州理工大学的罗伯特·H·格拉布斯教授开发一系列催化剂，用于烯烃歧化反应中的烯烃内部转化。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大的商业应用。这些进展包括发现新的无机络合物，显示出更高的活性或选择性。仍然存在一些限制：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，以及在有乙烯存在的情况下观察到的催化剂效率低。这些络合物以一种新的机制工作，随着对机制的更好理解，将为这些催化转化构建新的配体和络合物家族。诱导非环烯烃歧化反应的Ru络合物也可用于环烯烃的开环聚合。使用这些络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。由于理论原因，有一类特殊的聚合物可能具有有趣的应用，那就是没有末端的聚合物--环状聚合物。合成了一系列以环状单体为原料合成环状聚合物的Ru配合物。为了能够测试站得住脚的理论，需要的聚合物是纯循环的，没有线性污染。已经开发出一种方法，可以得到具有一定分子量范围的纯环状化合物。就更广泛的社会影响和效益而言，这些催化剂系统目前正被用于一系列成功的商业应用。需要使用这些催化剂关闭大环的新药物正在开发中，并正在进行临床试验。一座生物炼油厂正在建设中，该厂利用这些复合体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催化剂的聚合物已经在汽车市场上使用了多年。此外，正在生产用于建造大型机械设备的新型聚合物复合材料。

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.