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.*********

大多数增值化学品是通过催化作用由原料生产的。催化剂是能够改变化学反应速率并允许化学反应以更便宜且更环保的方式进行的化合物。催化涉及石油精炼、能源生产、农用化学品、聚合物和制药工业，甚至食品工业领域的各种工业过程。它直接或间接占工业化国家GDP的20-25%。然而，这些重要的过程大多数都是由后过渡金属（如铑和铂）催化的，这些金属价格昂贵且被认为是有毒的，这增加了合成和纯化的成本。****在过去的十年中，科学家们开始将主族化学应用于催化，以使用更便宜和毒性较小的金属，如铝和锌。开创性的进展包括发现受阻路易斯对对强非活化键的异解（离子）裂解及其在大量底物氢化中的应用，以及发现强键与还原主族化合物的氧化加成反应。尽管尚未以实际方式实施，但后一个过程可能是可将两种化合物偶联在一起的一类重要反应的关键。有关此过程的基本信息相当稀缺。****我们的研究计划旨在填补这一空白。我们将制备新的低价主族化合物家族，并研究这些还原中心上强西格玛键和多重键的活化。我们预计这些反应的结果将产生铝、锌、硅和锗的不寻常且大多是新的末端氧代、亚氨基和硫代衍生物。我们还将研究由氧化还原活性（非无害）配体支持的主基团中心的氧化加成及其逆（还原消除）反应的发生率。最后，在一个受生物学启发的项目中，我们将研究锌催化剂在通过廉价且环境友好的试剂（例如醇）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。对加拿大的主要好处将是高素质人员的培训和更高效、更清洁的催化系统的开发。*********