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，例如防御有毒自由基和 DNA 的生物合成，是由需要金属锰的酶来进行的。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，科学家们对该酶如何在锰中心周围创建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定变化如何控制化学反应性。需要确定这些系统的反应原理，以便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为普通化学课程开发公共海报项目，该项目具有展示学生学习和提高公众科学素养的双重目的。该项目还通过让研究生和本科生参加学术-工业联合会议和研讨会来提供独特的专业培训活动。在化学结构、动力学和机制 B 项目的资助下，堪萨斯大学的 Timothy Jackson 教授正在阐明基础理论控制 MnIII-羟基和 MnIII-烷基过氧配合物的断键和成键反应的原理。这些复合物模拟了各种锰依赖性酶（包括锰超氧化物歧化酶和锰脂氧合酶）机制中提出的中间体。 X 射线衍射、X 射线吸收、电子吸收和磁圆二色性方法与电子结构计算相结合，定义 MnIII-羟基和 MnIII-烷基过氧加合物的结构和电子性质，并确定如何调节这些配合物的物理性质通过路易斯酸、氢键和/或支持配体的变化。采用实验和计算相结合的方法来开发这些具有生物相关性的锰-氧中间体的新结构-反应性关系。 Jackson 教授积极致力于将 STEM 教育与推广相结合，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，并被认为是值得的通过使用基金会的智力优势和更广泛的影响审查标准进行评估来获得支持。

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

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

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.