Organometallic Reaction Mechanisms

有机金属反应机理

• 批准号: 0209476
• 负责人: Charles Casey
• 金额: $ 70万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-06-01 至 2007-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0209476&HistoricalAwards=false
• 关键词: Organometallic; Reaction; Mechanisms

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Charles P. Casey at the University of Wisconsin to develop an understanding of industrially-important metallocene polymerization catalysis and to pursue new synthetic paths to enediyne complexes that may facilitate the preparation of enediyne anticancer drugs. Metallocene catalysts have revolutionized the polymer industry and now account for the production of over 2 billion poinds of polyethylene a year. This research will look at a key step in the polymer chain-lengthening process by exploring the detailed structural dependence of alkene insertion into metallocene alkyls. A new synthetic reaction involving alkynyl carbene complexes, which juxtapose a metal-carbon double bond with a carbon-carbon triple bond, will be used to generate regioselective dimerization of the organic portion to yield enediyne complexes through a coupling of the terminal alkyne carbons. The initial focus will be on manganese compounds, which are more economical and more amenable to release of the metal ion. Since reactions of the alkynylcarbene complexes suggest a carbene-like reactivity at the remote alkynyl carbon, experiments will be undertaken to determine whether such complexes can react as if they were dicarbenes.The details of how catalysts add carbon groups in important industrial polymerization processes will be determined. A novel class of reagents that offers new routes to the preparation of an important class of anticancer drugs will be developed.

无机，生物无机和有机化学计划的这一奖项支持了威斯康星州大学的Charles P.凯西教授的研究，以了解工业上重要的茂金属聚合催化，并寻求新的合成途径，以促进烯二炔络合物的制备。 茂金属催化剂已经彻底改变了聚合物工业，现在每年生产超过20亿磅的聚乙烯。 这项研究将着眼于在聚合物链增长过程中的一个关键步骤，通过探索详细的结构依赖性烯烃插入到茂金属烷基。 一种新的合成反应，涉及炔基卡宾配合物，其中并列的金属-碳双键与碳-碳三键，将被用来产生区域选择性的有机部分的二聚反应，以产生烯二炔配合物通过末端炔碳的耦合。 最初的重点将是锰化合物，这是更经济和更容易释放的金属离子。 由于炔基卡宾配合物的反应表明在远侧炔基碳上具有类似卡宾的反应性，因此将进行实验以确定这种配合物是否可以像二卡宾一样反应。将确定催化剂如何在重要的工业聚合过程中添加碳基团的细节。 将开发一类新的试剂，为制备一类重要的抗癌药物提供新的途径。