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Studies on the mechanism of olefin-metathesis with Grubbs-Hoveyda complexes

Grubbs-Hoveyda配合物烯烃复分解反应机理研究

基本信息

批准号：
251237037
负责人：
Professor Dr. Herbert Plenio
金额：
--
依托单位：
Fachgebiet Anorganische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2014
资助国家：
德国
起止时间：
2013-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/251237037?language=en
关键词：
Studies mechanism olefin metathesis Grubbs

项目摘要

The present project is focusing on investigations of the mechanism of olefin-metathesis reactions with Grubbs-Hoveyda type complexes.Based on a model developed by us for the analysis of conversion-time data, it is now possible to determine the rate constants for catalyst activation k(act), the catalytic transformation k(cat) and catalyst decomposition (k(dec) of the catalytically active species. Especially k(cat) and k(dec) provide important information for catalyst optimization, since electronic and steric modifications at the catalytic center can now be analyzed separately for k(dec) and k(cat). It is a related aim of this project to learn, which stereoelectronic conditions determine the catalytic activity of Grubbs-Hoveyda complexes and which conclusions can be drawn based on the understanding of such factors for the preparation of improved catalysts.Furthermore, detailed studies on the mechanism of the dominating uni- and bimolecular catalyst deactivation pathways are planned for the species derived from Grubbs-Hoveyda type precatalysts.The role of ethene, which is formed as one reaction product of various olefin metathesis reactions, in the context of precatalyst activation, catalysis and catalyst decomposition is not clear yet. We thus propose to study the kinetics and the mechanism of ethene-induced reactions with Grubbs-Hoveyda type precatalysts.

本项目主要研究Grubbs-Hoveyda型络合物的烯烃复分解反应机理，根据我们建立的转化率-时间数据分析模型，可以确定催化剂活性组分的活化速率常数k（act）、催化转化速率常数k（cat）和催化分解速率常数k（dec）。特别是k（cat）和k（dec）为催化剂优化提供了重要信息，因为现在可以分别分析k（dec）和k（cat）在催化中心的电子和空间修饰。本项目的一个相关目的是了解哪些立体电子条件决定Grubbs-Hoveyda络合物的催化活性，以及基于对这些因素的理解可以得出哪些结论用于制备改进的催化剂。计划对来自Grubbs的物种详细研究主要的单分子和双分子催化剂失活途径的机理，作为各种烯烃复分解反应的一种反应产物形成的乙烯在预催化剂活化、催化和催化剂分解的情况下的作用尚不清楚。因此，我们建议研究的动力学和Grubbs-Hoveyda型预催化剂的乙烯诱导反应的机制。