Organometallic Reaction Mechanisms

该奖项在无机，生物无机和有机化学计划支持研究的有机金属反应的机制，由博士查尔斯P.凯西的化学系，威斯康星州大学麦迪逊。 三个不同的研究领域将继续进行：d-0钇和锆烯烃络合物的调查; π-炔丙基金属络合物的发展;和α-卡宾络合物的化学。选择的系统的第一个领域的调查将允许在金属中心的转化率和速率常数的测量，另外的金属烷基络合烯烃。 这些信息对于理解烯烃聚合的基本步骤和手性茂金属催化剂聚合的立体化学是重要的。 在第二个主题中，亲核试剂与π-炔丙基复合物的反应将被研究，以揭示产生这些物种的过程的基本理解。这些调查是针对这样的合成重要的反应，如双亲核加成炔丙基碳酸酯的理解。 最后，立体化学的膦与双卡宾配合物的加成将进行研究，沿着一些不寻常的配合物的形成，旨在提供有关的信息模式的关联金属与双键的碳化合物和有关使用环应变的变化，以有利于形成所需的产品。 有机化学在均相催化和开发合成有机化合物的新方法和新试剂方面已被证明是非常有用的。所选择的研究反应与具有重要商业意义的过程的行为有关。 本科生和研究生将参与这项研究。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on mechanisms of organometallic reactions by Dr. Charles P. Casey of the Chemistry Department, University of Wisconsin at Madison. Three distinct areas of research will be pursued: investigations of d-0 yttrium and zirconium olefin complexes; development of pi-propargyl metal complexes; and the chemistry of rhenium carbene complexes. The systems chosen for the first area of investigation will permit measurement of the rate of inversion at the metal center and the rate constants for the addition of a metal alkyl group to complexed alkenes. This information is important for understanding the fundamental steps in olefin polymerization and the stereochemistry of polymerization with chiral metallocene catalysts. In the second topic, reactions of nucleophiles with pi-propargyl complexes will be investigated in order to uncover a basic understanding of the processes that generate these species. These investigations are targeted toward an understanding of such synthetically important reactions as the double nucleophilic additions to propargyl carbonates. Finally, the stereochemistry of addition of phosphines with rhenium carbene complexes will be studied, along with the formation of some unusual complexes designed to give information about modes of association of metals with double-bonded carbon compounds and about using variation in ring strain to favor formation of desired products. Organometallic chemistry has proved to be very useful in homogeneous catalysis and in developing new methods and reagents for synthesis of organic compounds. The reactions chosen for investigation are relevant to the behavior of commercially important processes. Undergraduate and graduate students will be involved in the research.