Hydrogen Atom Transfer Reactivity of Unsymmetric Bimetallic Complex

不对称双金属配合物的氢原子转移反应性

• 批准号: 2246440
• 负责人: Shiyu Zhang
• 金额: $ 55万
• 依托单位: Ohio State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246440&HistoricalAwards=false
• 关键词: Hydrogen; Atom; Transfer; Reactivity; Unsymmetric

With support from the Chemical Structure, Dynamics & Mechanisms-B Program (CSDM-B) and the Chemical Synthesis (SYN) Program of the Chemistry Division, Shiyu Zhang of the Department of Chemistry at Ohio State University is developing model complexes to elucidate the influence of inequivalent environment on the reactivity of bimetallic centers in natural proteins. The goal of this research is to bridge the gap between metalloenzymes and synthetic catalysts designed to mimic enzymatic functions and unveil new design strategies for catalysts fundamental to energy, health, and environmental science. The research activities will be integrated with the training of undergraduate and graduate students in addressing interdisciplinary challenges with a combination of synthetic inorganic, spectroscopic, and theoretical methods. Outreach activities involving K-12 students will also be part of the funded project. In this project, two classes of new bimetallic complexes will be prepared to reproduce ubiquitous unsymmetric features of bimetallic active sites in nature, e.g., (i) inequivalent secondary coordination sphere, (ii) inequivalent primary coordination sphere, and (iii) unsymmetric metal binding (heterobimetallic center). New methods will be developed to quantify the degree of bimetallic differentiation and establish a set of metrics (hydrogen atom transfer kinetics, metal affinity, etc.) to help define success with the goal of improving our understanding of the metalloenzymes of interest. In Aim 1, dicopper model complexes with inequivalent features at the primary and secondary coordination sphere will be synthesized to understand if the degree of site-differentiation correlates with the rate of hydrogen atom transfer. In Aim 2, biomimetic heterobimetallic FeMn complexes will be developed to understand the formation of synthetic FeMn complexes. The reactivity of isostructural FeMn, FeFe, and MnMn bimetallic complexes toward oxygen activation and hydrogen atom transfer will be compared to understand the evolutionary implications of heterobimetallic active sites.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.

在化学系化学结构、动力学与机理-B计划（CSDM-B）和化学合成（SYN）计划的支持下，俄亥俄州立大学化学系的张世宇正在开发模型复合物，以阐明不等环境对天然蛋白质中双金属中心反应性的影响。这项研究的目标是弥合金属酶和模拟酶功能的合成催化剂之间的差距，并揭示能源、健康和环境科学基础催化剂的新设计策略。研究活动将与本科生和研究生的培训相结合，以结合合成无机、光谱和理论方法来应对跨学科挑战。涉及 K-12 学生的外展活动也将成为资助项目的一部分。 在该项目中，将制备两类新型双金属配合物，以重现自然界中普遍存在的双金属活性位点的不对称特征，例如（i）不等价的二级配位球，（ii）不等价的主配位球，以及（iii）不对称金属结合（异质双金属中心）。我们将开发新方法来量化双金属分化程度，并建立一套指标（氢原子转移动力学、金属亲和力等）来帮助定义成功，以提高我们对感兴趣的金属酶的理解。在目标 1 中，将合成在初级和次级配位层具有不等特征的二铜模型配合物，以了解位点分化程度是否与氢原子转移速率相关。在目标 2 中，将开发仿生异双金属 FeMn 络合物，以了解合成 FeMn 络合物的形成。将比较同结构 FeMn、FeFe 和 MnMn 双金属络合物对氧活化和氢原子转移的反应性，以了解异质双金属活性位点的进化影响。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。