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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.

在这个由美国国家科学基金会化学部化学结构、动力学和机理B项目资助的项目中，加州大学欧文分校化学系的Alan F. Heyduk教授正在开发一类新的配体，用于催化反应的发展。这项研究计划的主要目标是了解使氢原子和氢化物转移反应活性的基本配体性质，以便设计新的配位配合物，作为精细和商品化学合成中重要的还原反应的催化剂，以及丰富的化学原料（如一氧化碳和二氧化碳）的回收。该项目的基本性质是有机、有机金属和无机化学的界面，对所有教育水平的化学家都有广泛的吸引力，特别适合高级化学教育。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非无害配体平台因其在简单配位配合物中产生不确定电子性质的能力而在无机和有机金属化学中得到了很好的建立。这种性质已被用于多电子反应的催化剂、用于电荷转移的光敏剂以及具有先进电和磁性能的材料的合成。本文提出的工作将开发一种新型的非无罪配体，利用儿茶酚酸型配体的电子和质子转移能力来实现配体中心的氢原子转移（HAT）和氢化物转移（HT）反应性。在这个项目中，将研究两个相关的钳型配体，以回答几个广泛适用性的基本问题：(a)基于配体的HAT和HT反应性的热力学极限是什么？(b)基于配体的HAT和HT反应性的分子水平机制是什么？(c)是否可以利用配体结构和金属离子选择来调整这种基于配体的反应性，通过操纵热力学或动力学因素来选择性地支持HAT或HT反应性？该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。