CAS: Properties and Activation Mechanisms of Mn-hydroperoxo and Mn-alkylperoxo Complexes

在这项由化学系化学结构、动力学和机理B计划资助的项目中，堪萨斯大学化学系的蒂莫西·杰克逊教授正在开发和表征新的锰-氢过氧基和锰-烷基过氧基配合物，它们模仿了几种催化剂中的重要中间体。这项研究的目的是了解如何控制这些络合物的反应，这可能会导致新催化剂的设计。这项研究还将有助于更好地了解使用锰的生物酶。锰是一种富含地球的金属，它在催化反应中的使用增加有可能减轻一些环境影响和化学过程的成本。该项目位于无机化学和物理化学的交界处，为研究生和本科生提供了独特的培养体验。与这个项目相关的研究生将获得专业发展技能，在国家实验室进行实验，并通过同行评议的出版物、会议演讲和公共活动参与传播这项工作的结果。锰-氢过氧基配合物被提议作为生物和合成系统的中间体。尽管这些中间体很重要，但我们对这些络合物的基本性质和反应活性的了解还处于初级阶段。在这个项目中，我们将采用合成、动力学、光谱和计算相结合的方法来回答以下问题：1)锰(III)-过氧基配合物的基本物理性质是什么，这些性质是如何影响化学反应的？2)我们能否控制质子和/或电子传递到锰(III)-过氧基和锰(III)-过氧基配合物以启动特定的衰变途径？3)我们能否通过操纵锰(III)-烷基过氧基配合物的配位环境来影响O-O键的断裂机制？这项工作产生的新知识将促进对锰酶的更好理解，并可能产生用于设计新催化剂的原则。该奖项反映了NSF的法定使命，并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，被认为值得支持。

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 developing and characterizing new manganese-hydroperoxo and manganese-alkylperoxo complexes that mimic important intermediates in several catalysts. The goal of this research is to understand how to control the reactions of these complexes, which could lead to the design of new catalysts. This research will also contribute to a better understanding of biological enzymes that use manganese. Manganese is an earth-abundant metal, and its increased use in catalytic reactions has the potential to mitigate some of the environmental impacts and costs of chemical processes. This project lies at the interface of inorganic and physical chemistry, providing a unique training experience for graduate and undergraduate students. Graduate students associated with this project will gain professional development skills, perform experiments at National Labs, and be involved in disseminating the outcomes of this work through peer-reviewed publications, conference presentations, and public events.Manganese-hydroperoxo complexes are proposed as intermediates in both biological and synthetic systems. Despite the importance of such intermediates, our understanding of the fundamental properties and reactivity of these complexes is in its nascent stages. In this project, a combination of synthetic, kinetic, spectroscopic, and computational methods will be employed to answer the following questions: 1) What are the fundamental physical properties of manganese(III)-hydroperoxo complexes, and how do these properties influence chemical reactivity? 2) Can we control proton and/ or electron delivery to manganese(III)-hydroperoxo and manganese(III)-peroxo complexes to initiate specific decay pathways? 3) Can we manipulate the coordination environment of manganese(III)-alkylperoxo complexes to influence the O-O bond cleavage mechanism? The new knowledge generated from this work will foster a better understanding of manganese enzymes and could yield principles for use in the design of new catalysts.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.