Chemistry of Lewis Acidic Ligands: Hydrocarbon Functionalization, Borane "sigma-Complexes", and Catalytic Hydroboration

该奖项在无机，生物无机和有机 化学计划支持教授约翰F。哈特维希在 耶鲁大学 这项工作旨在揭示不寻常的反应， 金属硼基和硼烷化学基本原理 络合物通过评估与路易斯酸络合物的化学性质， 配体。 它致力于用金属硼基使烃官能化 络合物和合成与以下有关的金属茂硼烷络合物 催化硼氢化过程。 这些主题将作为案例 研究硼基配体和硼烷的亲电性如何 底物导致新的化学，尚未观察到更多 传统的有机金属体系。 相互作用的硼基中间体 与烃将被调查和取代基的影响， 选择性将被测量，以解决如何电泳 影响反应性。 早期金属硼烷的基本和实用方面， 将研究硼基物质。 稳定或增强的特性 这些络合物的反应性将根据它们的 在催化硼氢化中的作用。的手性选择性 茂钛催化硼氢化反应及单加成选择性 二烯将被研究。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports the research of Professor John F. Hartwig at Yale University. This work seeks to uncover unusual reactions and fundamental principles in the chemistry of metal-boryl and borane complexes by evaluating the chemistry of complexes with Lewis-acidic ligands. It endeavors to functionalize hydrocarbons with metal boryl complexes and to synthesize metallocene borane complexes related to catalytic hydroboration processes. These topics are to serve as case studies in how the electrophilicity of boryl ligands and borane substrates leads to new chemistry that has not been observed with more conventional organometallic systems. Boryl intermediates that interact with hydrocarbons will be investigated and substituent effects on selectivity will be measured in order to address how the electrophoricity of covalent ligands affects reactivity. Both fundamental and practical aspects of the early metal-borane and boryl species will be studied. The properties that stabilize or enhance the reactivity of these complexes will be studied with regard to their effects in catalytic hydroboration. The chiral selectivity of titanocene-catalyzed hydroboration and the selectivity of single addition to dienes will be studied.