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、生物无机和有机金属化学项目的支持下(i)研究不配位酸的氢与氢化物配体交换的动力学；（ii）寻找具有光学活性的氢化物配合物，探索其催化前手性底物对映选择性加氢的能力；（iii）探索含氮和含硫的环状试剂在锆氮氮嘧啶及其相关体系的M-C键上的插入反应，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；(4)考察用于激活烯烃聚合催化剂的亲电硼烷也可以作为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被用来发现产生反应性阳离子金属催化剂的重要新方法；（ii）侧重于了解氟化硼化合物的还原和提取特性的研究将对开发生产目前在几个工业设施中日常生产的聚合物的新方法产生直接影响。学生和博士后助理将接受催化和聚合物前体化学领域的优秀培训，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.