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

这个无机、生物无机和有机金属化学项目的奖项支持耶鲁大学John F. Hartwig教授的研究。这项工作旨在通过评价与刘易斯酸性配体配合物的化学反应，揭示金属-硼基和硼烷配合物的不寻常反应和基本化学原理。它致力于用金属硼基配合物功能化碳氢化合物，并合成与催化硼化过程有关的茂金属硼烷配合物。这些主题将作为案例研究，探讨硼基配体和硼烷底物的亲电性如何导致在更传统的有机金属系统中尚未观察到的新化学反应。与碳氢化合物相互作用的硼基中间体将被研究，取代基对选择性的影响将被测量，以解决共价配体的亲和性如何影响反应性。将研究早期金属硼烷和硼基的基本和实际方面。稳定或增强这些配合物的反应性的性质将在其催化硼氢化作用方面进行研究。研究了二茂钛催化硼氢化反应的手性选择性和二烯单加成反应的选择性。

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.