Electrophilic Attack on Coordinated Ligands Involved in Catalysis by Organometallic Complexes

哥伦比亚大学化学系的Jack Norton博士在化学系无机、生物无机和有机化学项目的支持下，（i）研究氢化物配体与未配位酸的氢交换的动力学;（ii）寻找光学活性氢化物络合物，并探索其催化前手性底物的对映选择性氢化的能力;（iii）探索含氮和含硫环状试剂插入锆氮杂环丙烷的M-C键的反应及相关体系，并利用其动力学和构型变化来控制氨基酸衍生物的立体化学;以及（iv）研究用于活化烯烃聚合催化剂的亲电硼烷也可以用作单电子氧化剂的可能性。该项目的意义是多方面的：（i）来自金属中心的氢化物受体将用于揭示产生反应性阳离子金属催化剂的重要新方法，以及（ii）研究集中在了解氟化硼烷化合物的还原和提取性能，这将直接关系到目前在几个工业领域日常生产中生产聚合物的新方法的开发。设施学生和博士后将在催化和聚合物前体化学领域接受优秀的培训，这种培训将有助于获得良好的工业工作。

Dr. Jack Norton of the Department of Chemistry, Columbia University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division to (i) examine the dynamics of hydride ligand exchange with hydrogens of uncoordinated acids; (ii) search for optically active hydride complexes and explore their ability to catalyze enantioselective hydrogenation of prochiral substrates; (iii) explore insertion reactions of nitrogen- and sulfur-containing cyclic reagents into the M-C bond of zirconaaziridines, and related systems, and exploit their dynamics and configurational changes to control the stereochemistry of amino acid derivatives; and (iv) examine the likelihood that electrophilic boranes used to activate olefin polymerization catalysts can also serve as one-electron oxidants.The significance of the project is manyfold: (i) hydride acceptors from metal centers will be utilized to uncover important new methods for generating reactive cationic metal catalysts, and (ii) studies focussed at understanding the reduction and abstraction properties of fluorinated borane compounds will have a direct bearing on the development of new methods to produce polymers currently in daily production in several industrial facilities. Students and post-doctorate associates will receive excellent training in the area of catalysis and polymer precursor chemistry, the kind of training that will facilitate obtaining good industrial jobs.