Mechanisms of Transition Metal Catalyzed Reactions in Hydrocarbons

本研究的重点涉及三个方面。首先，我们将用三种方法来了解Ru-亚烷基催化剂的失活模式：确定分解速率作为条件、添加剂和配体结构的函数。分解产物将用晶体结构和同位素标记进行研究。将准备各种新的1，3-disubstituted-4，5-dihydroimidazol-2-ylidene和相关系统，旨在抑制分解途径。其次，将开发利用嵌段聚合物技术制备纳米级共轭材料层和合成多层材料的方法。第三，将开发制备环状聚合物的方法，并将合成各种互锁聚合物拓扑结构。凭借这一奖项，有机和高分子化学计划和聚合物计划将支持加州理工学院化学和化学工程系罗伯特·H·格拉布斯博士的研究。格拉布斯教授将专注于开发一系列基于Ru的复分解催化剂，这些催化剂在基本水平上具有明确的参数，并且具有高效和选择性。此外，还将探索制造各种分散性非常窄的纳米级材料，特别是含有无机结构的材料所需的基本原理。还将开展针对环状聚合物的制备和表征的研究。该项目为学生的培训提供了一个极好的场所，并对制药业和材料科学产生了重要的更广泛的影响。

The foci of this research involve three areas. First, three methods will be used to understand the modes of deactivation of ruthenium alkylidene catalysts: Rates of the decomposition as a function of condition, additives and ligand structure will be determined. The products of decomposition will be investigated using crystal structures and isotopic labeling. A variety of new 1,3-disubstituted-4,5-dihydroimidazol-2-ylidene and related systems, designed to inhibit decomposition pathways, will be prepared. Second, methods for the preparation of nanoscale layers of conjugated materials and the synthesis of multilayer materials using block polymer techniques will be developed. Third, methods for the preparation of cyclic polymers will be developed and a variety of interlock polymer topologies will be synthesized.With this award, the Organic and Macromolecular Chemistry Program and the Polymers Program are supporting the research of Dr. Robert H. Grubbs in the Department of Chemistry and Chemical Engineering at the California Institute of Technology. Professor Grubbs will focus his work on developing a family of ruthenium based metathesis catalysts that have well defined parameters at the fundamental level and that are highly efficient as well as selective. Further, the fundamental principles required to produce a variety of nanoscaled materials with very narrow dispersities, especially materials containing inorganic structures will be explored. Research aimed at the preparation and characterization of cyclic polymers will also be carried out. The project presents an excellent venue for the training of students and has important broader impacts for the pharmaceutical industry and materials science.