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

无机、生物无机和有机金属项目的这一研究奖支持了布兰代斯大学的奥列格·奥泽罗夫教授探索由一系列刚性钳形配体支撑的过渡金属络合物的化学工作。模块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的变化。所设计的金属络合物将进行新的催化转化，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本探索协同进行：为简单和氧化加成反应生成统一标度，可能观察到过渡金属甲烷络合物和金氢化物络合物，以及研究金属中心严重不饱和的电子后果。研究成果将被用于制作教育材料，并将予以传播。这项工作的一个组成部分是与其他机构的同事合作，特别是与本科院校的同事合作。梅里马克学院的安东尼·费尔南德斯教授将获得一个研究固态氧化加成反应的子奖。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。过渡金属催化在许多对现代社会具有重要意义的工业过程中是不可或缺的。络合支撑配体可用于稳定均相过渡金属催化剂。使用一系列模数可变的刚性结构的配体将有助于更好地了解单个供体位置对金属络合物整体反应性的影响。

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.