Copper Sulfide Model Complexes for Small Molecule Activation

用于小分子活化的硫化铜模型配合物

• 批准号: 9172495
• 负责人: Neal P Mankad
• 金额: $ 19.08万
• 依托单位: UNIVERSITY OF ILLINOIS AT CHICAGO
• 依托单位国家: 美国
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-08-01 至 2021-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/9172495
• 关键词: Active Sites; Address; Aerobic; Architecture; Area; Biological; Biological Models; Biological Sciences; Carbon; Carbon Dioxide; Carbon monoxide dehydrogenase; Chemicals; Chemistry; Communities; Complex; Copper; Coupling; Data; Environment; Environmental Pollutants; Enzymes; Exhibits; Fostering; Future; Goals; Health; Human; Individual; Knowledge; Lead; Ligands; Literature; Mediating; Metalloproteins; Metals; Methods; Mission; Modeling; Molybdenum; Nature; Outcome; Oxidation-Reduction; Oxygen; Pathway interactions; Positioning Attribute; Process; Public Health; Reaction; Regulation; Research; Role; Scheme; Site; Structure; Study models; Sulfides; Sulfur; System; Work; base; biological systems; catalyst; computer studies; covalent bond; design; electronic structure; frontier; greenhouse gases; improved; innovation; knowledge base; nitrous oxide reductase; novel; oxidation; research study; small molecule; stoichiometry

Atmospheric concentrations of CO2 and N2O, the #1 and #2 most consequential greenhouse gases on earth, both are regulated in part by metalloproteins containing multimetallic copper-sulfide active sites. The nature of multimetallic cooperativity in these active sites and the role of the conserved copper-sulfide structure as it relates to enzymatic function are poorly understood. The objective of this application is to use synthetic model studies to understand the role of nature's privileged copper-sulfide cluster motif in facilitating multimetallic cooperativity associated with multielectron/multiproton regulation of both CO2 and N2O. Our central hypothesis is that the bridging sulfur atoms both covalently mediate redox coupling of the individual metal sites, and also participate in covalent activation of the small molecule substrates. Our rationale for pursuing this objective is that it will inform and motivate future catalyst designs for crucial multielectron redox transformations that depend on CO2, N2O, and other small-molecule substrates. We will work towards achieving the overall objective by pursuing the following specific aims: 1) develop synthetic methods for tetracopper, dicopper, and copper-molybdenum clusters with single sulfur atom bridges; 2) conduct combined spectroscopic- computational studies of electronic structure across different cluster oxidation states; 3) investigate stoichiometric and catalytic reactions with CO2, N2O, and related model substrates. The proposed research is significant because the synthetic difficulty in accessing such model complexes has precluded their careful study until now, and so our team is in a unique position to make important contributions that advance the field vertically. This approach is innovative because it gives us a unique ability to address biologically relevant coordination chemistry questions with structurally faithful model systems constructed through rational design. Attaining the objective of the proposal will positively impact the chemical community, as multielectron/multiproton transformations of small molecules are crucial not only to biological systems but also to many frontier areas including alternative energy conversion and storage.

大气中二氧化碳和N2O的浓度，这两种气体是地球上最严重的温室气体， 两者都受到含有多金属硫化铜活性中心的金属蛋白的部分调控。的性质 这些活性中心上的多金属协作性以及保守的铜-硫化物结构在其中的作用 与酶功能有关的知识知之甚少。此应用程序目标是使用合成模型 了解自然界特权铜-硫化物簇状基序在促进多金属中的作用的研究 与二氧化碳和N2O的多电子/多质子调节相关的协作性。我们的中心假设 是桥硫原子既以共价方式调节各个金属位置的氧化还原偶联，又 参与小分子底物的共价活化。我们追求这一目标的理由是 它将为关键的多电子氧化还原转化提供信息并激励未来的催化剂设计，这些转化 依靠二氧化碳、N2O和其他小分子底物。我们将努力实现总体目标 目的通过以下具体目标：1)开发四铜、二铜和三氯乙烷的合成方法 含单硫原子桥的铜钼团簇；2)进行联合光谱研究。 团簇不同氧化态电子结构的计算研究；3)研究 与二氧化碳、N2O和相关模型底物的化学计量和催化反应。拟议的研究是 这很重要，因为访问这种模型复合体的合成困难排除了他们仔细的 到目前为止，我们的团队处于独特的地位，能够为推动该领域的发展做出重要贡献 垂直的。这种方法是创新的，因为它给了我们一种独特的能力来处理与生物相关的 通过合理的设计，构建结构合理的模型体系，协调化学问题。 实现该提案的目标将对化学界产生积极影响，因为 小分子的多电子/多质子转换不仅对生物系统至关重要，而且对生物系统也是至关重要的。 到许多前沿领域，包括替代能源转换和储存。