SusChEM: Water Oxidation by Homogeneous Manganese Catalysts

SusChEM：均相锰催化剂的水氧化

• 批准号: 1566258
• 负责人: Jeremy Smith
• 金额: $ 40.5万
• 依托单位: Indiana University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-06-15 至 2020-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1566258&HistoricalAwards=false
• 关键词: SusChEM; Water; Oxidation; Homogeneous; Manganese

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Jeremy M. Smith, Department of Chemistry and Biochemistry, Indiana University, investigates how well-defined manganese catalysts convert water into oxygen. Nature has learned to convert water to oxygen using visible light. This process is called photosynthesis and uses manganese in a complicated biological protein. In this project, smaller managanese compounds are being studied both to provide basic information on photosynthetic oxygen formation and to provide new catalysts, based on inexpensive, abundant metals, for use in the laboratory or by the chemical industry. An important part of the project involves the training of students in bioinorganic and energy chemistry. This project utilizes synthetic, spectroscopic and physical studies to investigate the mechanism of water oxidation by manganese macrocyclic complexes. The modular catalyst design allows for the introduction of functional groups, enabling systematic studies into the effect of proton and hydrogen atom transport as well as metal cofactors on catalyst performance. A family of manganese pyridinophane compounds serve as functional models for the oxygen evolving complex of Photosystem II. This work sets out to: (1) experimentally validate a computationally-proposed mechanism for water oxidation by these complexes, (2) determine the impact of pyridinophane stereoelectronic properties on catalytic selectivity and activity, and (3) delineate the effect of the second coordination sphere on catalytic activity, including the presence of proton and hydrogen atom relays, and redox-innocent metals. Spectroscopic, reactivity and mechanistic investigations of these species provide insights relevant to the biological water oxidation mechanism, particularly the key O-O bond forming step. Compounds are characterized by standard physical methods of X-ray diffraction, NMR, EPR, and IR, while catalytic behavior is investigated by a combination of electrochemical measurements and standard mechanistic probes.

在这个由化学系化学合成项目资助的项目中，印第安纳大学化学与生物化学系的 Jeremy M. Smith 教授研究了明确的锰催化剂如何将水转化为氧气。大自然已经学会利用可见光将水转化为氧气。这个过程称为光合作用，并在复杂的生物蛋白质中使用锰。在该项目中，正在研究较小的锰化合物，以提供光合作用氧气形成的基本信息，并提供基于廉价、丰富金属的新催化剂，供实验室或化学工业使用。该项目的一个重要部分涉及对学生进行生物无机和能源化学方面的培训。该项目利用合成、光谱和物理研究来研究锰大环配合物氧化水的机制。模块化催化剂设计允许引入官能团，从而能够系统研究质子和氢原子传输以及金属辅助因子对催化剂性能的影响。吡啶芬锰化合物家族可作为光系统 II 放氧复合物的功能模型。这项工作的目的是：（1）通过实验验证计算提出的这些配合物氧化水的机制，（2）确定吡啶芬立体电子性质对催化选择性和活性的影响，以及（3）描述第二配位的影响催化活性领域，包括质子和氢原子中继以及氧化还原无害金属的存在。这些物种的光谱、反应性和机理研究提供了与生物水氧化机制相关的见解，特别是关键的 O-O 键形成步骤。通过 X 射线衍射、NMR、EPR 和 IR 等标准物理方法对化合物进行表征，同时通过电化学测量和标准机械探针相结合来研究催化行为。

项目成果

Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

Fe(VI) 双(亚氨基) 配合物的结构和光谱表征

• DOI: 10.1126/science.abd3054
• 发表时间: 2020-10
• 期刊: Science
• 影响因子: 56.9
• 作者: Martinez, Jorge L.;Lutz, Sean A.;Yang, Hao;Xie, Jiaze;Telser, Joshua;Hoffman, Brian M.;Carta, Veronica;Pink, Maren;Losovyj, Yaroslav;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base Resistance

铁催化烯烃异构化中的二态反应性赋予γ-碱电阻

• DOI: 10.1021/jacs.0c07300
• 发表时间: 2020-09
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Lutz, Sean A.;Hickey, Anne K.;Gao, Yafei;Chen, Chun;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Stabilization of the Dinitrogen Analogue, Phosphorus Nitride

二氮类似物氮化磷的稳定化

• DOI: 10.1021/acscentsci.0c00944
• 发表时间: 2020-09
• 期刊: ACS Central Science
• 影响因子: 18.2
• 作者: Martinez, Jorge L.;Lutz, Sean A.;Beagan, Daniel M.;Gao, Xinfeng;Pink, Maren;Chen, Chun;Carta, Veronica;Moënne;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Ligand Substituent Effects in Manganese Pyridinophane Complexes: Implications for Oxygen-Evolving Catalysis

吡啶芬锰锰配合物中的配体取代基效应：对析氧催化的影响

• DOI: 10.1021/acs.inorgchem.7b02421
• 发表时间: 2017-11
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Xu, Song;Bucinsky, Lukas;Breza, Martin;Krzystek, J.;Chen, Chun;Pink, Maren;Telser, Joshua;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

A flexible, redox-active macrocycle enables the electrocatalytic reduction of nitrate to ammonia by a cobalt complex

灵活的氧化还原活性大环化合物能够通过钴配合物将硝酸盐电催化还原为氨

• DOI: 10.1039/c8sc00721g
• 发表时间: 2018-01
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Xu, Song;Ashley, Daniel C.;Kwon, Hyuk;Ware, Gabrielle R.;Chen, Chun;Losovyj, Yaroslav;Gao, Xinfeng;Jakubikova, Elena;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.