Mechanisms of Transition Metal Catalyzed Reactions in Hydrocarbons

在化学系有机动力学项目的支持下，加州理工学院的Robert Grubbs教授将继续研究能够影响广泛应用的催化剂系列。该催化剂显示出高水平的活性和选择性，其理解来自于机理和结构功能关系的研究。在下一个授予期间，将开发和探索新的方法来合成配体，这将有助于从根本上了解控制这些系统效率的因素。从这些研究中，将产生一系列N-杂环卡宾的有效方法，这些方法可用于烯烃复分解以外的许多催化过程。尽管活性复分解催化剂已经由钌、锇和铱制备，但迄今为止，甚至没有基于铁的中等有效的复分解催化剂的报道。将制备和研究支持和稳定铁亚烷基的配体系统，以确定从钌催化剂中吸取的一些经验教训是否可以应用于铁基系统。拟议研究的另一个目标是探索合成新形式聚乙烯（PE）的途径，用于开发和测试结构-性能关系模型。将开发新的路线来完善线性和单分散的PE，继续探索环状PE，并开发新的方法来合成超支化PE。已经建立了合作，以充分表征和比较这些拓扑结构不同的材料的性能。此外，开发用于两种烯烃之间的官能团交换（官能团复分解）的催化剂的新策略，类似于烯烃复分解，其涉及两种烯烃之间的片段交换。这一策略将为烯烃的氧化、氮丙啶化和水合提供新的途径。特别强调的将是一种催化剂的发展，为反马尔可夫加成水烯烃。为了帮助这些调查，快速筛选技术将被使用，基本的机械研究将被执行。这个由加州理工学院Grubbs教授提出的建议将产生新的聚合物材料，工业界和学术界的其他团体将使用这些材料来探索结构-性能关系。过去的计划产生了超过65篇出版物和14项与烯烃复分解化学相关的专利。这些出版物要么直接由NSF资助，要么通过使用NSF资金开发的催化剂而成为可能。NSF资助的项目的学术影响力通过被排名在引用最多的项目中的前两名来证明，每篇论文有90次引用。该研究计划产生了一些学生，他们现在是主要学术和工业机构的杰出研究人员。它带来了来自世界各地的博士后研究员和学生，并支持2-4名本科生为期十周，让他们接触学术研究。Grubbs教授的研究是许多工业过程的基础，并在美国创造了新的就业机会。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Robert Grubbs at The California Institute of Technology will continue to work on a family of catalysts that have been able to impact a broad range of applications. The catalysts have displayed high levels of both activity and selectivity, the understanding of which has resulted from studies of mechanisms and structure function relationships. During the next granting period, new methods will be developed and explored for the synthesis of ligands that will aid in the fundamental understanding of the factors that control the efficiency of these systems. Out of these studies will come an efficient method for generating an array of N-heterocyclic carbenes that can be used in many catalytic processes beyond olefin metathesis. Although active metathesis catalysts have been prepared from ruthenium, osmium and iridium, to date there are no reports of even a moderately efficient metathesis catalyst based on iron. Ligand systems that should support and stabilize iron alkylidenes will be prepared and investigated to determine if some of the lessons learned from ruthenium catalysts can be applied to iron-based systems. Another objective of the proposed research is to explore routes to the synthesis of new forms of polyethylene (PE) to be used to develop and test models of structure-property relationships. New routes will be developed to perfect linear and monodispersed PE, continue the exploration of cyclic PEs, and develop new approaches to the synthesis of hyper-branched PE. Collaborations have been established for the full characterization and comparison of the properties of each of these topologically diverse materials. Additionally, a new strategy to develop catalysts for the interchange of functional groups (functional group metathesis) between two olefins, similar to olefin metathesis, which involves the interchange of fragments between two olefins. This strategy will provide new routes for the oxidation, aziridination, and hydration of olefins. Special emphasis will be on the development of a catalyst for the anti Markovnikov addition of water to olefins. To aid in these investigations, rapid screening techniques will be used and fundamental mechanistic studies will be carried out.This proposal by Professor Grubbs at The California Institute of Technology will produce new polymeric materials that other groups both in industry and academia will use to explore structure-property relationships. The past program produced over 65 publications and 14 issued patents related to olefin metathesis chemistry. These publications were either directly funded by NSF or were made possible by catalysts developed using NSF funding. The academic impact of the NSF funded program is demonstrated by being ranked in the top two of most cited programs with 90 citations per paper. The research program has produced a number of students who are now outstanding researchers in major academic and industrial institutions. It brings postdoctoral fellows and students from around the world, and supports 2-4 undergraduates for a ten week period, exposing them to academic research. Professor Grubbs' research is the basis for a number of industrial processes and is creating new employment opportunities in the US.