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.

俄亥俄州州立大学化学系的张世玉在化学部化学结构、动力学机制-B计划（CSDM-B）和化学合成（SYN）计划的支持下，正在开发模型复合物，以阐明不等效环境对天然蛋白质中双中心反应性的影响。这项研究的目标是弥合金属酶和合成催化剂之间的差距，旨在模拟酶的功能，并揭示新的设计策略，催化剂的基础能源，健康和环境科学。研究活动将与本科生和研究生的培训相结合，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学生的外联活动也将是资助项目的一部分。 在这个项目中，将制备两类新的双金属配合物，以再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)不等价的次级配位球，（ii）不等价的初级配位球，和（iii）不对称的金属结合（杂原子中心）。将开发新的方法来量化氢原子分化的程度，并建立一套指标（氢原子转移动力学，金属亲和力等）。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球处具有不等价特征的双铜模型络合物，以了解位点分化的程度是否与氢原子转移的速率相关。在目标2中，将开发仿生杂铁锰配合物，以了解合成的铁锰配合物的形成。同构FeMn，FeFe和MnMn复合物对氧活化和氢原子转移的反应性将进行比较，以了解异质结活性sites.This奖项的演变影响反映了NSF的法定使命，并已被认为是值得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的支持。