Electrophilic Attack on Coordinated Ligands Involved in Catalysis by Organometallic Complexes

该奖项在无机，生物无机和有机化学 项目支持Jack R博士的研究。诺顿的化学 科罗拉多州立大学化学系， 有机金属过渡金属配合物，重点是行为 氢化物配体在对映选择性反应中的作用。 第一个项目是 开发一种NMR方法来检测氢化物配体的存在下， 为了测试质子转移的热力学驱动力， 同位素效应，并开发光学活性氢化物络合物， 可以将氢化物转移到基底的相对的前手性面， 有很大的不同率。 质子加到氧中-和 将遵循含氮配体。 在一个相关项目中， 由二茂锆促进的氨基酸的对映选择性合成将 特别注意提高产量， 反应的选择性。 催化Zr-C键的质子断裂 CO将被研究，将使用氮烯锆络合物， 制备对映体富集的氨基醇。 该项目有两个主题：金属氧化物的反应， 锆化学 金属氢化物研究旨在开发 将氢从金属氢化物转移到有机化合物的新方法 同时保持所需的立体定向。 锆 化合物是用于其中C-C和 形成C-N键。 这些结果将有助于理解 氢与金属化合物反应的基本行为， 开发新的有机合成试剂。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research by Dr. Jack R. Norton of the Chemistry Department, Colorado State University, on the reactivity of organometallic transition metal complexes, with emphasis on the behavior of hydride ligands in enantioselective reactions. The first project is to develop an NMR method to detect hydride ligands in the presence of acid in order to test the thermodynamic driving force for proton tranfer isotope effects, and to develop optically active hydride complexes that can transfer hydride to opposite prochiral faces of a substate at substantially different rates. Proton addition to oxygen- and nitrogen-containing ligands will be followed. In a related project, enantioselective synthesis of amino acids promoted by zirconocenes will be investigated with particular attention on increasing the yield and selectivity of the reaction. Protic cleavage of Zr-C bonds catalyzed by CO will be studied as will the use of zirconium nitrene complexes to prepare enantiomerically enriched amino alcohols. This project has two main themes: reactions of metal hydrides and zirconium chemistry. The metal hydride studies are designed to develop new ways to transfer hydrogen from a metal hydride to an organic compound while maintaining a desired stereospecific orientation. The zirconium compounds are potentially useful agents for reactions in which C-C and C-N bonds are formed. The results will be relevant to understanding the fundamental behavior of hydrogen reactions with metal compounds and to developing new reagents for organic synthesis.