Organometallic Reaction Mechanisms

该奖项由无机、生物无机和有机金属化学项目颁发，支持威斯康星大学Charles P. Casey教授的研究，以发展对工业上重要的茂金属聚合催化的理解，并寻求新的合成途径来合成烯二因复合物，这可能有助于制备烯二因抗癌药物。茂金属催化剂已经彻底改变了聚合物工业，现在每年的聚乙烯产量超过20亿分。本研究将通过探索烯烃插入茂金属烷基的详细结构依赖关系来研究聚合物链延长过程中的关键步骤。一个新的合成反应涉及炔基碳配合物，将金属-碳双键和碳-碳三键并置，将通过末端炔碳的偶联产生有机部分的区域选择性二聚化，从而产生烯二炔配合物。最初的重点将放在锰化合物上，锰化合物更经济，更容易释放金属离子。由于炔基碳配合物的反应表明在远端炔基碳上具有类碳的反应活性，因此将进行实验以确定这种配合物是否能像二羰基一样反应。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被确定。一类新的试剂将为一类重要的抗癌药物的制备提供新的途径。

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.