Late-Metal Alkyne and Metallacyclobutene Reaction Chemistry

加州大学圣地亚哥分校化学系的 Joseph O'Connor 博士在化学系无机、生物无机和有机金属化学项目的支持下，对金属环丁烯络合物的合成、结构阐明以及形成和反应的机理方面进行了研究。金属环丁烯-乙烯基碳烯互变似乎在这些物质的化学中发挥着重要作用。因此，将通过计算化学研究控制金属环丁烯稳定性的因素，并通过实验研究互变的差向异构和酸碱化学。将利用金属卡宾配合物与重氮炔的反应来开发生产金属环丁烯的新路线，并将探索钴环丁烯的热解作为生产环丙烯的路线。将研究基于邻环丁烯的催化化学。除了揭示这些复合物的新合成方法和应用之外，拟议的研究还将解决其合成和反应的立体控制问题。该项目涉及一类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晚期过渡元素。主要目标是发展对可用于合成和催化有机化学的反应的机理理解。因此，新方法对于药物的制备很有价值。该项目将用于教育和培训本科生、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.