Organometallic Reaction Mechanisms

无机化学、生物无机化学和金属有机化学项目的这一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理的研究。将开展三个截然不同的研究领域：d-0Y和锆烯类络合物的研究；pi-炔丙基金属络合物的开发；以及Re-卡宾络合物的化学。为第一个研究区选择的系统将允许测量金属中心的烯烃解离速率和反转速率。这些信息对于理解手性茂金属催化剂聚合的立体化学是很重要的。我们将研究三种合成丙炔丙基配合物的方法，以及亲核剂与这些配合物的反应，这已被证明在有机合成中是有用的。本课程将研究Re卡宾络合物中加入盐酸的立体化学，以及一些不寻常的络合物的形成，这些络合物旨在提供关于金属与双键碳化合物的结合模式的信息，以及关于利用环应变的变化来促进所需产品的形成。有机金属化学已被证明在均相催化和开发合成有机化合物的新方法和试剂方面非常有用。被选择用于研究的反应与商业上重要的过程的行为相关。

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 alkene dissociation and the rate of inversion at the metal center. This information is important for understanding the stereochemistry of polymerization with chiral metallocene catalysts. Three methods of synthesis of the pi-propargyl complexes will be investigated, as well as the reaction of nucleophiles with these complexes, which have been shown to be useful in organic synthesis. The stereochemistry of addition of HCl to 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.