CAREER: Interplay of metal coordination and ligand-based reactivity in complexes of oligopyrrolic fragments

有了这个职业奖，化学合成项目支持了亚利桑那大学Elisa Tomat教授的基础研究。Tomat教授将使用选定的低聚吡咯化合物来研究过渡金属配合物中金属配位和基于配体的氧化还原化学的相互作用。本文主要研究了低聚吡咯的合成及其配体性质。这些新物质的灵感来自细菌生物合成和血红素氧化代谢产生的天然化合物。对作为电子源或储存器的配体系统的研究为反应途径的工程设计提供了新的途径，从而为开发在化学和制药工业中具有潜在高影响的多功能可调催化剂创建了一个概念框架。Tomat教授将把这个项目的研究和教育内容整合到化学发现中，这是一个面向中学生的新拓展项目。通过一系列旨在强调日常经验与化学进步之间联系的研讨会，化学发现为中学生提供了基于发现的体验，通过实验捕捉STEM领域的创造力。托马特教授与当地学区和特许学校建立了合作关系。《化学发现》触及了一个在科学领域代表性不足的弱势群体。除了生产新颖的教育资源外，化学发现还通过一个单元的本科课程，吸引本科生参与外展研讨会的发展。该项目为中学生提供了一个与大学生互动讨论科学观察的机会，促进了对STEM领域高等教育的追求。在本研究中，将开发合成二吡咯和三吡咯配体的新方法。由于低聚吡咯的电子结构可以通过合成操作高度调节，因此可以获得一系列的配位和氧化还原性质。本研究旨在促进配合物的设计，利用配体平台和金属中心作为电子交换的场所。这些类低聚吡啶配体的配位和氧化还原化学将被研究，特别是关于催化应用的潜在兴趣的晚期过渡金属。氧化还原性质的趋势将与基于配体的单电子交换的反应性相关。

With this CAREER Award, the Chemical Synthesis program is supporting fundamental research of Professor Elisa Tomat at the University of Arizona. Professor Tomat will employ selected oligopyrrolic compounds to investigate the interplay of metal coordination and ligand-based redox chemistry in transition metal complexes. This work focuses on the synthesis and ligand properties of oligopyrroles. These new substances are inspired by naturally occurring compounds derived from bacterial biosynthesis and from the oxidative metabolism of heme. The investigation of ligand systems which act as electron sources or reservoirs offers new avenues for the engineering of reactivity pathways, thereby creating a conceptual framework for the development of versatile tunable catalysts of potentially high impact in the chemical and pharmaceutical industry. Professor Tomat will integrate the research and educational components of this project within Chemistry Discovery, a new outreach program for middle school students. Through a series of workshops aimed at highlighting the connections between everyday experience and chemistry advances, Chemistry Discovery provides middle school students with a discovery-based experience that captures the creativity of the STEM fields through experiments. Professor Tomat has established partnerships with local school districts and charter schools. Chemistry Discovery reaches an underprivileged community which is underrepresented in the sciences. In addition to the production of novel educational resources, Chemistry Discovery engages undergraduate students in the development of outreach workshops through a one-unit undergraduate course offering. The program promotes the pursuit of higher education in the STEM fields by providing an opportunity for middle-school students to discuss scientific observations while interacting with college students.In this research, new methods are to be developed for the synthesis of dipyrrolic and tripyrrolic ligands. Because the electronic structure of oligopyrroles is highly tunable by synthetic manipulations, a range of coordination and redox properties will be accessed. This research seeks to facilitate the design of complexes which enlist both the ligand platform and the metal center as sites of electron exchange. The coordination and redox chemistry of these classes of oligopyrrolic ligands will be investigated, in particular with respect to late transition metals of potential interest for catalytic applications. Trends in redox properties will be correlated with reactivity profiles involving ligand-based one-electron exchanges.