Late-Metal Alkyne and Metallacyclobutene Reaction Chemistry

Joseph O'Connor博士，加州大学圣地亚哥分校化学系，受化学系无机、生物无机和有机金属化学项目的支持，对金属环丁烯复合物的合成、结构解析和形成和反应的机理方面进行了研究。金属环丁烯-乙烯基碳的相互转化似乎在这些物种的化学反应中起着重要作用。因此，本文将利用计算化学方法研究控制金属环丁烯稳定性的因素，并通过实验研究金属环丁烯的外显异构化和相互转化的酸碱化学。利用金属羰基配合物与重氮炔反应制备金属环丁烯的新途径将得到开发，钴环丁烯的热裂解反应将作为制备环丙烯的新途径。以钯环丁烯为基础的催化化学研究。除了发现这些配合物的新合成方法和应用外，拟议的研究将解决它们的合成和反应的立体控制问题。本项目涉及一类被称为金属环丁烯的有机金属化合物的制备和反应性的研究。这些研究感兴趣的例子包含后期转变因素。主要目标是发展对可能在合成和催化有机化学中使用的反应的机理理解。因此，这些新方法将对药物的制备有价值。该项目将用于教育和培养本科生、研究生和博士后。

Dr. Joseph O'Connor, Chemistry Department, University of California - San Diego, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division for an investigation of the synthesis, structural elucidation, and mechanistic aspects of the formation and reactions of metallacyclobutene complexes. A metallacyclobutene-vinylcarbene interconversion appears to play an important role in the chemistry of these species. Consequently, the factors that control the stability of the metallacyclobutenes will be studied by computational chemistry and the epimerization and acid-base chemistry of the interconversion will be investigated experimentally. New routes to metallcyclobutenes will be developed employing reactions of metal carbene complexes with diazoalkynes and thermolysis of cobalt cyclobutenes will be explored as a route to cyclopropenes. Catalytic chemistry based on pallacyclobutenes will be investigated. In addition to uncovering new synthetic approaches to and applications of these complexes, the proposed studies will address stereocontrol of their synthesis and reactions. This project involves investigations of the preparation and reactivity of a class of organometallic compound known as metallacyclobutenes. The examples of interest for these studies contain late transition elements. The major objective is the development of a mechanistic understanding of reactions that may find use in synthetic and catalytic organic chemistry. As such, the new methods will be valuable to the preparation of pharmaceuticals. The project will serve to educate and train undergraduate, graduate and postdoctoral student.