SusChEM: Group-Transfer Reactions of Low-Coordinate Metals

SusChEM：低配位金属的基团转移反应

• 批准号: 1266281
• 负责人: Richard Jordan
• 金额: $ 50.5万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-04-01 至 2017-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1266281&HistoricalAwards=false
• 关键词: SusChEM; Group; Transfer; Reactions; Low

With this award from the Chemical Synthesis (SYN) Program, Professor Gregory Hillhouse at the University of Chicago will carry out fundamental studies on the coordination and organometallic chemistry of low-coordinate first-row metals in various oxidation states. The primary objective of this work is to develop synthetic routes to new types of reactive late-transition metal complexes that can be used to carry out new atom- and group-transfer reactions that will enable efficient, atom-economical chemical transformations. These studies will help elucidate fundamental properties of inorganic molecules, particularly those with metal-ligand multiple bonds that stimulate novel reactivity. This chemistry will impact both stoichiometric and catalytic synthetic organic transformations. Group 10 metal complexes have widespread synthetic application in catalytic coupling reactions that form new carbon-carbon (C-C) and C-X single bonds, and this project will focus on developing useful methods for forming C=C, C=N, C=O, and C=S bonds (or other double bonds) utilizing nickel and other first-row metals. This research will explore, using experiment and theory, the coordination and organometallic chemistry of very low-coordinate metal complexes that form multiple bonds with imido and carbene ligands (LnNi=NR and LnNi=CR2), as well as non-traditional 2- and 3-coordinate open-shell, late-metal systems. This research will provide a solid, fundamental understanding of the chemistry of group transfer reactions involving metals that will impact applied areas of synthetic inorganic chemistry and catalysis, as well as organic synthesis and thus contribute to sustainability. In addition to the scientific contributions, this project will contribute to the training of the next generation of scientists and teachers by providing experience in interdisciplinary work, honing research skills, and exposure to both target-oriented and fundamental research that will empower coworkers to make transformative contributions to US chemical research endeavors. Specific activities directed toward education and outreach, with emphasis on the chemical challenges of the twenty-first century, are planned. The research team will include scientists at all educational levels: faculty, postdoctoral researchers, graduate, undergraduate, and high-school students. Participation of persons from underrepresented groups, which recently have included Hispanic, African-American, sight-disabled, and female coworkers, will be actively encouraged.

通过化学合成（SYN）计划的奖项，芝加哥大学的格雷戈里·希尔豪斯（Gregory Hillhouse）教授将对各种氧化状态中低坐标第一行金属的协调和有机金属化学进行基础研究。这项工作的主要目的是开发合成途径，以新类型的反应性晚期金属络合物，可用于进行新的原子和组转移反应，以实现有效的原子 - 经济化学转化。这些研究将有助于阐明无机分子的基本特性，尤其是具有刺激新反应性的金属配体多个键的金属配体键。该化学将影响化学计量和催化合成有机转化。第10组金属络合物在形成新的碳碳（C-C）和C-X单键的催化耦合反应中具有广泛的合成应用，并且该项目将着重于开发使用镍和其他第一再环金属的C = C，C = C = C = C = C = C = C = N，C = O = O = O = S = S键（或其他双键）。这项研究将使用实验和理论探索非常低坐标金属络合物的配位和有机金属化学，这些化学络合物与Imido和Carbene配体形成多个键（LNNI = NR和LNNI = CR2），以及非交易的2和3型式式式式开放式，后壳，后壳，后壳，后壳。这项研究将对涉及金属的群体转移反应的化学反应提供牢固的基本了解，这些反应将影响合成无机化学和催化的应用领域，以及有机合成，从而有助于可持续性。除科​​学贡献外，该项目还将通过提供跨学科工作，磨练研究技能以及对目标和基础研究的经验来为下一代科学家和教师的培训做出贡献。计划着针对教育和外展的特定活动，重点是二十一世纪的化学挑战。研究团队将包括所有教育水平的科学家：教职员工，博士后研究人员，研究生，本科生和高中生。将积极鼓励来自代表性不足的团体的人的参与，包括西班牙裔，非裔美国人，观光者和女同事。