Main group compounds for bond activation and catalysis

用于键活化和催化的主族化合物

• 批准号: RGPIN-2017-05231
• 负责人: Nikonov, Georgii
• 金额: $ 5.39万
• 依托单位: Brock University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=660970
• 关键词: Main; group; compounds; bond; activation

Most value-added chemicals are produced from feedstock materials by means of catalysis. Catalysts are compounds that change the rate of chemical reactions and allow for chemical reactions to be carried out in a less expensive and more environmentally benign way. Catalysis is involved in a variety of industrial processes in the petroleum refining, energy production, agrochemical, polymer, and pharmaceutical industries, even food industry sectors. It accounts, directly or indirectly, for 20-25% of GDP of industrialised countries. However, most of these important processes are catalysed by late transition metals, such as rhodium and platinum, which are expensive and are recognized to be toxic, which contributes to the cost of synthesis and purification.****Over the past decade, scientists have begun applying main-group chemistry to catalysis to use cheaper and less toxic metals such as aluminum and zinc. Seminal advances include the discovery of heterolytic (ionic) cleavage of strong non-activated bonds by Frustrated Lewis Pairs and its application to hydrogenation of a vast array of substrates and the discovery of oxidative addition reaction of strong bonds to reduced main-group compounds. Although it has not yet been implemented in a practical way, the latter process is potentially a key to an important class of reactions that can couple two compounds together. The fundamental information about this process is rather scarce.****Our research programme is aimed at filling this gap. We shall prepare new families of low-valent main group compounds and investigate activation of strong sigma bonds and multiple bonds on these reduced centres. We expect that unusual and mostly new terminal oxo, imido, and sulfido derivatives of aluminum, zinc, silicon, and germanium will be produced as a result of these reactions. We shall also study the incidence of oxidative addition and its reverse (reductive elimination) reactions from main group centres supported by redox-active (non-innocent) ligands. And, finally, in a biologically inspired project, we shall study the applicability of zinc catalysts to practical reduction of synthetically useful carbonyl compounds by inexpensive and environmentally benign reagents, such as alcohols.****The main benefit to chemistry will be the advancement of scientific knowledge. The main benefit to Canada will be the training of Highly Qualified Personnel and development of more efficient and cleaner catalytic systems.*********

大多数附加值化学品是由原料通过催化方法生产的。催化剂是一种化合物，它可以改变化学反应的速度，并允许以更便宜和更环保的方式进行化学反应。催化作用涉及石油精炼、能源生产、农用化学品、聚合物和制药行业，甚至食品工业部门的各种工业过程。它直接或间接地占工业化国家GDP的20%-25%。然而，这些重要过程中的大多数都是由后过渡金属催化的，如铑和铂，这些金属价格昂贵，而且被认为是有毒的，这增加了合成和提纯的成本。在过去的十年里，科学家们已经开始将主基化学应用于催化，以使用更便宜、毒性较低的金属，如铝和锌。开创性的进展包括发现了受挫的Lewis对对强非活化键的异解(离子)断裂，并将其应用于一系列底物的氢化，以及发现了强键与还原主基化合物的氧化加成反应。尽管它还没有以实际的方式实施，但后一种过程可能是一类重要的反应的关键，这些反应可以将两种化合物耦合在一起。关于这一过程的基本信息相当稀缺。*我们的研究方案旨在填补这一空白。我们将准备新的低价主族化合物家族，并研究这些还原中心上强sigma键和多键的活化。我们预计，这些反应将产生不寻常的、主要是新的铝、锌、硅和锗的末端氧、亚胺和硫代衍生物。我们还将研究氧化还原活性(非无辜)配体支持的主要基团中心的氧化加成及其反向(还原消除)反应的发生率。最后，在一个生物启发的项目中，我们将研究锌催化剂在通过廉价和对环境友好的试剂(如醇)实际还原合成有用的羰基化合物方面的适用性。化学的主要好处将是科学知识的进步。加拿大的主要好处将是培训高素质的人员和开发更高效、更清洁的催化系统。