Organometallic Reaction Mechanisms

这个无机、生物无机和有机金属化学项目的奖项支持威斯康星大学麦迪逊分校化学系的查尔斯·p·凯西博士对有机金属反应机制的研究。将进行三个不同领域的研究：d-0钇和锆烯烃配合物的研究；异丙基金属配合物的研制以及碳铼配合物的化学性质。为第一个研究领域选择的系统将允许测量金属中心的反转速率和金属烷基加成到络合烯烃的速率常数。这一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具有重要意义。在第二个主题中，将研究亲核试剂与pi-丙炔配合物的反应，以揭示对产生这些物质的过程的基本理解。这些研究的目的是为了了解这些重要的合成反应，如双亲核添加到丙炔碳酸酯。最后，我们将研究磷化氢与碳铼配合物加成的立体化学，以及一些特殊配合物的形成，这些配合物旨在提供金属与双键碳化合物的结合模式的信息，以及利用环应变的变化来促进所需产物的形成。有机金属化学在均相催化和开发合成有机化合物的新方法和试剂方面已被证明是非常有用的。选择用于研究的反应与商业上重要的过程的行为有关。本科生和研究生将参与研究。

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.