SusChEM: Electronic Structure and Reactivity of Peroxo- and Hydroxomanganese Compounds

SusChEM：过氧和羟基锰化合物的电子结构和反应性

• 批准号: 1565661
• 负责人: Timothy Jackson
• 金额: $ 41.6万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565661&HistoricalAwards=false
• 关键词: SusChEM; Electronic; Structure; Reactivity; Peroxo

In this project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Timothy Jackson of the Department of Chemistry at the University of Kansas is investigating new manganese peroxo and hydroxo complexes with interesting chemical reactivity. The goal of this research is to determine how the structures of these manganese complexes can be controlled to impart a desired reaction. This knowledge could be used to reduce the cost and environmental footprint of chemical transformations and will advance understanding of manganese enzymes in humans, plants, and bacteria. The project lies at the interface of inorganic, physical and biological chemistry, and provides a training experience for graduate and undergraduate students. Trips to national laboratories to perform X-ray absorption experiments afford training in synchrotron radiation, including radiation safety training. This research is disseminated to the general public via presentations at University Orientation Days, the University Mini-College, and Science on Tap. In these forums, a broad, general audience engages with on-going chemical research. Spectroscopic and theoretical methods used in this research is incorporated into graduate and undergraduate courses. This research has relevance to sustainable chemistry because it uses less toxic and more abundant manganese complexes.Manganese(III)-peroxo adducts are frequently proposed as intermediates in the formation of high-valent manganese-oxo species in synthetic oxidation catalysts. Manganese(III)-hydroxo motifs are known to participate in biologically important proton-coupled electron-transfer reactions. However, the influence of geometric and electronic structure on the reactivity of these compounds is not well defined. Specific aims of the project include: 1) investigation of the O-O bond activation pathways of a manganese(III)-peroxo adduct support by an oxidatively robust ligand; 2) exploration of ligand effects on the reductive activation of manganese(III)-peroxo adducts; and 3) a systematic variation of the ligand field of manganese(III)-hydroxo complexes to develop correlations between electronic structure perturbations and chemical reactivity. Through this work, molecular-level insight into the activation of peroxomanganese(III) species for oxygen (O)-O bond cleavage through chemical and electrochemical pathways are developed. In addition, the proton-coupled electron transfer reactions of mid-valent hydroxomanganese(III) species are explored. In an undergraduate bioinorganic course,students will develop video modules describing relevant physical methods. The methods used in this research are incorporated into graduate and undergraduate courses. The results of this work are disseminated broadly through University and community outreach activities.

在这个由化学部化学结构、动力学机制B计划资助的项目中，堪萨斯大学化学系的蒂莫西杰克逊教授正在研究具有有趣化学反应性的新锰过氧和氢氧配合物。 本研究的目的是确定如何控制这些锰络合物的结构以实现所需的反应。 这些知识可用于降低化学转化的成本和环境足迹，并将促进对人类，植物和细菌中锰酶的了解。该项目位于无机，物理和生物化学的接口，并为研究生和本科生提供培训经验。前往国家实验室进行X射线吸收实验提供了同步辐射培训，包括辐射安全培训。这项研究是通过在大学迎新日，大学迷你学院和科学自来水介绍传播给公众。在这些论坛中，广泛的普通观众参与正在进行的化学研究。本研究中使用的光谱和理论方法被纳入研究生和本科生课程。这项研究与可持续化学有关，因为它使用毒性较小且更丰富的锰络合物。锰（III）-过氧加合物经常被提议作为合成氧化催化剂中高价锰氧物种形成的中间体。锰（III）-羟基基序参与生物学上重要的质子耦合电子转移反应。 然而，几何和电子结构对这些化合物的反应性的影响并没有很好地定义。该项目的具体目标包括：1）通过氧化稳定配体研究锰（III）-过氧加合物载体的O-O键活化途径; 2）探索配体对锰（III）-过氧加合物还原活化的影响;以及3）锰（III）-羟基络合物配体场的系统变化，以开发电子结构扰动和化学反应性之间的相关性。 通过这项工作，分子水平上的洞察到激活过氧锰（III）物种的氧（O）-O键断裂通过化学和电化学途径的发展。 此外，质子耦合的电子转移反应的中间价羟锰（III）物种进行了探索。 在本科生物无机课程中，学生将开发描述相关物理方法的视频模块。在这项研究中使用的方法被纳入研究生和本科课程。这项工作的成果通过大学和社区外联活动广泛传播。

项目成果

Electronic Structure and Magnetic Properties of a Titanium(II) Coordination Complex

钛(II)配位络合物的电子结构和磁性

• DOI: 10.1021/acs.inorgchem.0c00311
• 发表时间: 2020
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Zolnhofer, Eva M.;Wijeratne, Gayan B.;Jackson, Timothy A.;Fortier, Skye;Heinemann, Frank W.;Meyer, Karsten;Krzystek, J.;Ozarowski, Andrew;Mindiola, Daniel J.;Telser, Joshua
• 通讯作者: Telser, Joshua