Exploring Hydrogen-Atom- and Hydride-Transfer Non-Innocent Ligands

探索氢原子和氢化物转移非无害配体

基本信息

批准号：
1800386
负责人：
Alan Heyduk
金额：
$ 42万
依托单位：
University of California-Irvine
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-09-01 至 2023-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800386&HistoricalAwards=false
关键词：
Exploring Hydrogen Atom Hydride Transfer

项目摘要

In this project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division of NSF, Professor Alan F. Heyduk of the Department of Chemistry at the University of California, Irvine is developing a new class of ligand for use in the development of catalytic reactions. The principal goal of this research program is to understand the fundamental ligand properties that enable hydrogen-atom and hydride transfer reactivity so new coordination complexes can be designed to serve as catalysts in reduction reactions of importance in fine and commodity chemical synthesis and in the recycling of abundant chemical feedstocks such as carbon monoxide and carbon dioxide. The fundamental nature of the project, which lies at the interface of organic, organometallic and inorganic chemistry, is broadly appealing to chemists at all education levels and is particularly well-suited to advanced levels of chemical education. Towards this end, the project includes a strong component that encourages underrepresented groups to pursue advanced degrees in STEM research areas. Redox-active or redox non-innocent ligand platforms are well established in inorganic and organometallic chemistry for their ability to engender adventitious electronic properties in simple coordination complexes. Such properties have been exploited in catalysts for multi-electron reactivity, in photosensitizers for charge-transfer applications, and in the synthesis of materials with advanced electrical and magnetic properties. The work proposed herein will develop a new type of ligand non-innocence that leverages both electron- and proton-transfer abilities of catecholate-type ligands to achieve ligand-centered hydrogen-atom transfer (HAT) and hydride transfer (HT) reactivity. In this project, two related pincer-type ligands will be examined to answer several fundamental question of broad applicability: (a) What are the thermodynamic limits of ligand-based HAT and HT reactivity? (b) What is (are) the molecular-level mechanism(s) of ligand-based HAT and HT reactivity? (c) Can ligand architecture and metal ion selection be used to tailor this ligand-based reactivity to favor selectively HAT or HT reactivity through the manipulation of thermodynamic or kinetic factors?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.

在该项目中，由NSF化学结构，动态和机制B计划资助，加利福尼亚大学化学系的化学部门教授Alan F. Heyduk教授正在开发一种新的配体，用于开发催化反应。该研究计划的主要目的是了解启用氢原子和氢化物转移反应性的基本配体特性，因此可以设计新的配位络合物作为催化剂的催化剂，以减少在细和商品化学化学合成中的重要性，以及在丰富的化学物质原料中循环中的碳二氧化碳和碳二氧化碳和碳二氧化物。该项目的基本性质在于有机，有机金属和无机化学的界面，广泛吸引了所有教育水平的化学家，并且特别适合高级化学教育水平。为此，该项目包括一个强大的组成部分，鼓励代表性不足的群体在STEM研究领域攻读高级学位。氧化还原活性或氧化还原的非中性配体平台在无机和有机金属化学中已经很好地确定了它们在简单的协调复合物中产生不良电子性能的能力。在催化剂中利用了此类特性，以用于多电子反应性，用于电荷转移应用的光敏剂以及具有先进电气和磁性特性的材料的合成中。本文提出的工作将开发出一种新型的配体非源源，该配体不一致，利用了儿茶酸酯型配体的电子和质子转移能力，以实现以配体为中心的氢原子转移（HAT）和氢化物转移（HT）反应性。在该项目中，将检查两个相关的钳子型配体以回答广泛适用性的几个基本问题：（a）基于配体的HAT和HT反应性的热力学限制是什么？（b）什么是（）基于配体HAT和HT反应性的分子级机制？（c）是否可以使用配体建筑和金属离子选择来调整这种基于配体的反应性，以通过操纵热力学或动力学因素来选择性地选择HAT或HT反应性？该奖项反映了NSF的法定任务，并认为通过基金会的智力和更广泛的影响，可以通过评估来审查CRITERIA，并认为通过评估的支持值得通过评估。