Bond Forming Reactions at High Coordinate and Polynuclear Transition Metal Clusters

该项目的目标是在无机，生物无机 和有机化学计划是为了发现新的方法， 使用过渡金属作为模板， 化学键这种研究在设计中很重要， 催化剂的化学合成和建模的行动， 金属酶 该项目的重点是还原偶联，氧化偶联， 偶联和对映体特异性C-C键形成（例如， 催化共轭加成）之间的紧密定位 过渡金属配合物中的配体。高坐标早 具有线性配体（CO，CNR，-CCR， 等等）。提供还原偶联反应通道 化学.氧化偶联将使用 通过融合两个氧代中心的多金属支架 三角形金属聚集体（M3 O，M=Fe，Mn，Cr，Ru）或两个 di（mu 2）dioxomanganese单位，后者提供新的 模拟分子氧中四锰中心的方法 光系统进化复合体II。新的催化剂和 将进行化学计量的C-C键形成反应 在与两种相同或不同的金属键合的配体之间 中心举行的极点对称（包含两对 氮供体）或不对称（例如，含有一对 膦供体和一组三个氮供体） 双核大环这些研究的结果将 深入了解高坐标和多金属 过渡金属中心促进键形成反应， 有机金属和生物无机化学，并应导致 新分子的基本利益以及合成 效用

The objective of this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is to discover new ways to use transition metals as templates for the formation of chemical bonds. Such research is important in the design of catalysts for chemical synthesis and in modelling the action of metalloenzymes. The focus of the project is on reductive coupling, oxidative coupling and enantiospecific C-C bond formation (e.g., catalytic conjugate addition) between closely positioned ligands in transition metal complexes. High coordinate early transition metal complexes with linear ligands (CO, CNR, -CCR, etc.) provide a reaction channel for reductive coupling chemistry. Oxidative coupling will be explored using the polymetallic scaffold provided by fusing two oxo-centered triangular metal aggregates (M3O, M=Fe, Mn, Cr, Ru) or two di(mu2)dioxomanganese units, the latter affording a new approach to modelling the tetramanganese center in the dioxygen evolving complex of photosystem II. New catalytic and stoichiometric C-C bond forming reactions will be carried out between ligands bonded to two identical or disparate metal centers held at the poles of symmetric (containing two pairs of nitrogen donors) or asymmetric (e.g., containing a pair of phosphine donors and a set of three nitrogen donors) binucleating macrocycles. The results of these studies will afford insights into how high coordinate and polymetallic transition metal centers promote bond forming reactions in organometallic and bioinorganic chemistry and should lead to new molecules of fundamental interest as well as synthetic utility.