Mechanisms of Alkene-Metal Oxide Interactions

烯烃-金属氧化物相互作用的机制

• 批准号: 9312650
• 负责人: Kevin Gable
• 金额: $ 27万
• 依托单位: Oregon State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-07-15 至 1996-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9312650&HistoricalAwards=false
• 关键词: Mechanisms; Alkene; Metal; Oxide; Interactions

This grant from the Organic Dynamics Program supports the work of Professor Gable at Oregon State University to investigate mechanisms and synthetic applications of organometallic reactions relevant to catalysis. The key question to be addressed is whether olefins react with only the oxygen of metal oxides in a concerted fashion or whether an intermediate metallaoxetane is formed. Based on preliminary data on ethylene, norbornene, and norbornadiene, the initial systems to be studied are reversible reactions of olefins with various rhenium oxides. The objective is to determine quantitative structure-reactivity relationships, which include the thermodynamics, kinetics, isotope effects, and the Thorton analysis to probe the symmetry of the transition state. These mechanistic studies will then be extended to other alkene oxidants, in particular osmium tetraoxide. %%% In this project Professor Gable will investigate the mechanism of the oxidation reaction of olefins with metal oxides and thereby provide much needed insight into an area which is of fundamental importance. The main targets are to develop quantitative structure-reactivity relationships and probing transition states for rhenium oxides, which studies will then be extended to other oxidants in the pursuit of new catalysts for application in high volume industrial processes.

有机动力学计划的这笔赠款支持以下工作： 俄勒冈州州立大学的盖博教授来调查 有机金属反应机理及合成应用 与催化有关。要解决的关键问题是 烯烃是否仅与金属氧化物中的氧反应， 或者中间体金属氧杂环丁烷是否 形成了根据乙烯、异戊烯和 降冰片二烯，要研究的初始系统是可逆的 烯烃与各种氧化物的反应。客观 是确定定量的结构-反应性关系， 包括热力学、动力学、同位素效应， 用Thorton分析来探讨相变的对称性 状态这些机制研究将扩展到其他 烯烃氧化剂，特别是四氧化锇。 %%% 在这个项目中，盖博教授将研究 烯烃与金属氧化物的氧化反应， 提供了对一个基本领域的急需的洞察力， 重要性主要目标是发展量化 结构-反应性关系和探测过渡态 对于氧化物，研究将扩展到其他 氧化剂在追求新的催化剂的应用在高 大批量工业生产。