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

无机化学、生物无机化学和金属有机化学项目的这一奖项支持耶鲁大学约翰·F·哈特威格教授的研究。这项工作试图通过评估具有Lewis-酸性配体的络合物的化学来揭示金属-硼基和硼烷络合物化学中的不寻常反应和基本原理。它致力于用金属硼基络合物功能化碳氢化合物，并合成与催化加氢硼化过程相关的茂金属硼烷络合物。这些主题将作为案例研究，研究硼基配体和硼烷底物的亲电性如何导致更传统的有机金属系统所未观察到的新化学。将研究与碳氢化合物相互作用的硼基中间体，并测量取代基对选择性的影响，以解决共价配体的电泳性如何影响反应活性。我们将研究早期金属--硼烷和硼基物种的基础和实用方面。稳定或提高这些络合物的反应活性的性质将根据它们在催化氢化硼化反应中的作用进行研究。研究了茂钛催化的硼氢化反应的手性选择性和二烯烃的单加成选择性。

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.