SusChEM: Group-Transfer Reactions of Low-Coordinate Metals

芝加哥大学的Gregory Hillhouse教授获得了化学合成（SYN）项目的奖金，将对各种氧化态低配位第一排金属的配位和有机金属化学进行基础研究。这项工作的主要目标是开发新型反应性过渡后金属配合物的合成路线，这些配合物可用于进行新的原子和基团转移反应，从而实现高效，原子经济的化学转化。这些研究将有助于阐明无机分子的基本性质，特别是那些具有金属配体多重键的分子，这些键可以激发新的反应性。这种化学反应将影响化学计量学和催化合成有机转化。10族金属配合物在催化偶联反应中有广泛的合成应用，形成新的碳-碳（C-C）和C- x单键，本项目将重点开发利用镍和其他第一排金属形成C=C， C=N， C=O和C=S键（或其他双键）的有用方法。本研究将通过实验和理论探讨与亚胺和碳配体（LnNi=NR和LnNi=CR2）形成多重键的极低配位金属配合物的配位和有机金属化学，以及非传统的2和3坐标开壳、晚金属体系。这项研究将为涉及金属的基团转移反应的化学提供坚实的基础理解，这将影响合成无机化学和催化以及有机合成的应用领域，从而有助于可持续发展。除了科学贡献外，该项目还将通过提供跨学科工作经验，磨练研究技能，以及接触目标导向和基础研究，为下一代科学家和教师的培训做出贡献，从而使同事能够为美国化学研究事业做出变革性的贡献。计划开展针对教育和宣传的具体活动，重点是二十一世纪的化学挑战。研究团队将包括各个教育层次的科学家：教师、博士后、研究生、本科生和高中生。将积极鼓励来自代表性不足群体的人员参与，这些群体最近包括西班牙裔、非裔美国人、视障人士和女同事。

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.