Geometric and Electronic Structure Contributions to Bond-breaking and Bond-making Reactions of Mid-valent Manganese-Oxygen Complexes

几何和电子结构对中价锰氧配合物断键和成键反应的贡献

• 批准号: 1900384
• 负责人: Timothy Jackson
• 金额: $ 39万
• 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: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900384&HistoricalAwards=false
• 关键词: Geometric; Electronic; Structure; Contributions; Bond

In many organisms, important chemical reactions, such as defense against toxic free radicals and the biosynthesis of DNA, are performed by enzymes that require the metal manganese. A thorough understanding of the functions of these enzymes requires knowledge of intermediates formed during the chemical reactions. At present, scientists have a limited understanding of how the enzyme creates an environment around the manganese center to control the reactivity of particular intermediates. In this project, Professor Timothy Jackson of the University of Kansas is using synthetic chemistry to make models of these enzyme intermediates, with the goal of understanding how particular variations to the manganese environment control chemical reactivity. The identification of principles of reactivity for these systems are required to allow scientists to both better understand the function of the manganese enzymes and to use these enzymes as inspiration to develop synthetic counterparts. Professor Jackson is also actively engaged in developing public poster projects for a General Chemistry course that serve a dual purpose of displaying student learning and increasing public scientific literacy. This project also offers unique, professional training activities by having graduate and undergraduate students participate in joint academic-industrial meetings and workshops.With funding from the Chemical Structure, Dynamics, and Mechanisms B program, Professor Timothy Jackson of the University of Kansas is elucidating foundational principles governing the bond-breaking and bond-making reactions of MnIII-hydroxo and MnIII-alkylperoxo complexes. These complexes mimic intermediates proposed in the mechanisms of various manganese-dependent enzymes, including manganese superoxide dismutase and manganese lipoxygenase. X-ray diffraction, X-ray absorption, electronic absorption, and magnetic circular dichroism methods are combined with electronic structure computations to define structural and electronic properties of MnIII-hydroxo and MnIII-alkylperoxo adducts and determine how the physical properties of these complexes are modulated by Lewis acids, hydrogen-bonds, and/ or variations in supporting ligands. The combined experimental and computational approach is employed to develop new structure-reactivity relationships for these manganese-oxygen intermediates of biological relevance. Professor Jackson is actively engaged in combining STEM education and outreach by increasing public scientific literacy through the incorporation of STEM outreach projects in a General Chemistry course, in support of the broader impacts of this project.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在许多生物体中，重要的化学反应，如防御有毒自由基和DNA的生物合成，都是由需要金属锰的酶来完成的。要彻底了解这些酶的功能，需要了解化学反应过程中形成的中间体。目前，科学家对酶如何在锰中心周围创造环境以控制特定中间体的反应性的了解有限。在这个项目中，堪萨斯大学的蒂莫西杰克逊教授正在使用合成化学来制作这些酶中间体的模型，目的是了解锰环境的特殊变化如何控制化学反应性。需要确定这些系统的反应性原理，以使科学家能够更好地了解锰酶的功能，并利用这些酶作为开发合成对应物的灵感。杰克逊教授还积极参与开发公共海报项目的一般化学课程，服务于展示学生学习和提高公众科学素养的双重目的。此外，本项目还通过研究生和本科生参加学术与产业的联合会议和研讨会，提供独特的专业培训活动。堪萨斯大学的蒂莫西·杰克逊教授在化学结构、动力学和机理B项目的资助下，阐明了MnIII-羟基和MnIII-烷基过氧络合物的键断裂和键形成反应的基本原理。这些配合物模拟各种锰依赖性酶，包括锰超氧化物歧化酶和锰脂氧合酶的机制中提出的中间体。X-射线衍射，X-射线吸收，电子吸收，和磁性圆二色性方法相结合的电子结构计算来定义的结构和电子性质的锰III-羟基和锰III-烷基过氧加合物，并确定这些配合物的物理性质是如何调制的刘易斯酸，氢键，和/或变化的支持配体。实验和计算相结合的方法来开发新的结构-反应性的关系，这些锰氧中间体的生物相关性。杰克逊教授积极参与STEM教育和推广相结合，通过将STEM推广项目纳入普通化学课程来提高公众的科学素养，以支持该项目的更广泛影响。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Electrochemical Formation and Reactivity of a Mn‐Peroxo Complex Bearing an Amido N5 Ligand

带有氨基 N5 配体的 Mn-Peroxo 配合物的电化学形成和反应活性

• DOI: 10.1002/celc.202200112
• 发表时间: 2022
• 期刊: ChemElectroChem
• 影响因子: 4
• 作者: Massie, Allyssa A.;Kostopoulos, Nikolaos;Grotemeyer, Elizabeth N.;Noël, Jean‐Marc;Jackson, Timothy A.;Anxolabéhère‐Mallart, Elodie
• 通讯作者: Anxolabéhère‐Mallart, Elodie

Electronic Structure and Magnetic Properties of a Low-Spin Cr II Complex: trans -[CrCl 2 (dmpe) 2 ] (dmpe = 1,2-Bis(dimethylphosphino)ethane)

低自旋 Cr II 配合物的电子结构和磁性：反式 -[CrCl 2 (dmpe) 2 ] (dmpe = 1,2-双(二甲基膦基)乙烷)

• DOI: 10.1021/acs.inorgchem.1c02471
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Zolnhofer, Eva M.;Opalade, Adedamola A.;Jackson, Timothy A.;Heinemann, Frank W.;Meyer, Karsten;Krzystek, J.;Ozarowski, Andrew;Telser, Joshua
• 通讯作者: Telser, Joshua

Probing the Mechanism for 2,4′-Dihydroxyacetophenone Dioxygenase Using Biomimetic Iron Complexes

利用仿生铁配合物探讨 2,4â²-二羟基苯乙酮双加氧酶的机制

• DOI: 10.1021/acs.inorgchem.1c00167
• 发表时间: 2021
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Banerjee, Atanu;Li, Jia;Molenda, Monika A.;Opalade, Adedamola A.;Adhikary, Amitava;Brennessel, William W.;Malkhasian, Aramice Y.;Jackson, Timothy A.;Chavez, Ferman A.
• 通讯作者: Chavez, Ferman A.

Controlling the Reactivity of a Metal-Hydroxo Adduct with a Hydrogen Bond

• DOI: 10.1021/jacs.1c06199
• 发表时间: 2021-09-08
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Opalade, Adedamola A.;Hessefort, Logan;Jackson, Timothy A.
• 通讯作者: Jackson, Timothy A.

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