Rigid Chelating Ligands as Tools for Discovery of New Reactions and Applications in Catalysis

这个无机、生物无机和有机金属项目的研究奖支持了布兰代斯大学奥列格·奥泽罗夫教授的工作，他探索了由一系列刚性钳型配体支撑的过渡金属配合物的化学性质。模块化结构和刚性将允许支持配体与过渡金属中心的电子相互作用的逻辑和系统变化。设计的金属配合物将有针对性地催化新的转化，如硼-硼键的形成和铑催化的碳-碳和碳杂原子偶联反应。对催化应用的追求将与基础探索协同进行：生成简单和氧化加成反应的统一尺度，可能观察过渡金属甲烷配合物和金氢化物配合物，以及研究金属中心严重不饱和的电子后果。研究结果将用于制作教育材料，并加以散发。工作的一个组成部分是与其他机构的同事合作，特别是主要是本科生。梅里马克学院的安东尼·费尔南德斯教授将获得一项研究固态氧化加成反应的次级奖励。将组织一次区域本科生研究研讨会，以促进本科生研究并加强区域化学界的联系。在现代社会的许多重要工业过程中，过渡金属催化是不可缺少的。螯合支撑配体可用于稳定均相过渡金属催化剂。使用一系列模块化可变的、刚性构造的配体，可以更好地理解单个给体位点对金属配合物总体反应性的影响。

This research award in the Inorganic, Bioinorganic and Organometallic program supports work by Professor Oleg Ozerov at Brandeis University to explore the chemistry of transition metal complexes supported by a series of rigid pincer-type ligands. The modular construction and the rigidity will allow for logical and systematic variation of the electronic interactions of the supporting ligands with the transition metal centers. New catalytic transformations by the designed metal complexes will be targeted, such as boron-boron bond formation and rhodium-catalyzed carbon-carbon and carbon-heteroatom coupling reactions. The pursuit of catalytic applications will take place in synergy with fundamental explorations: generation of a unified scale for reactions of simple and oxidative addition, possible observation of a transition metal methane complex and of a gold hydride complex, and studies of electronic consequences of severe unsaturation at the metal center. Research results will be used to create educational materials, which will be disseminated. An integral part of the work is the collaboration with colleagues at other, especially primarily undergraduate, institutions. Prof. Anthony Fernandez of Merrimack College will be supported through a subaward to investigate solid-state oxidative addition reactions. A regional undergraduate research symposium will be organized to promote undergraduate research and enhance ties in the regional chemistry community. Transition metal catalysis is indispensable in many industrial processes of importance to modern society. Chelating supporting ligands can be used to stabilize homogeneous transition metal catalysts. Using a series of modularly variable, rigidly constructed ligands will permit the development of better understanding of the influence of the individual donor sites on the overall reactivity of the metal complex.