From Bond Activation to Catalysis

从键活化到催化

• 批准号: RGPIN-2014-04766
• 负责人: Budzelaar, Peter
• 金额: $ 1.12万
• 依托单位: University of Manitoba
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=611231
• 关键词: Bond; Activation; Catalysis

Homogeneous catalysis is the preferred method for high-precision, minimal-waste synthesis of high-value-added chemical products such as pharmaceuticals. Many catalysts contain a metal atom surrounded by a "protective coat", the ligand; ligand variation allows tuning of the catalyst performance. My research program is aimed at understanding steps of chemical reactions at metals, and at quantifying how ligand variation can be used to influence those steps. Within my group, we use both computational and experimental techniques, which allows us to probe reaction mechanisms in great detail. In one research theme, we study ligands that can function as "electron reservoirs", temporarily storing electrons and then releasing them when needed to make reactions happen. In another theme, we look at ligands that bind strongly to their metal but occupy so much space that the metal is prevented from attaining its preferred surrounding, thus increasing its reactivity. In both themes, we have in previous work discovered new bond breaking and making chemistry that so far is still stoichiometric. In the coming grant period we aim to convert this into true catalysis. If successful, this would lead for theme 1 to new, cleaner options for creating carbon skeletons, the backbones of organic compounds (including pharmaceuticals). In theme 2, success in catalysis would afford easier and cleaner access to a range of organosilicon compounds, which find applications in organic synthesis as well as in the preparation of materials.

均相催化是高精度、最少废物合成高附加值化学产品（例如药品）的首选方法。许多催化剂含有被“保护层”（配体）包围的金属原子；配体变化可以调节催化剂性能。我的研究项目旨在了解金属化学反应的步骤，并量化配体变化如何影响这些步骤。在我的小组中，我们使用计算和实验技术，这使我们能够非常详细地探讨反应机制。在一个研究主题中，我们研究了可以充当“电子库”的配体，暂时存储电子，然后在需要时释放电子以发生反应。在另一个主题中，我们着眼于与金属牢固结合但占据大量空间的配体，从而阻止金属到达其首选的周围环境，从而提高其反应性。在这两个主题中，我们在之前的工作中发现了新的化学键断裂和化学反应，迄今为止仍然是化学计量的。在接下来的资助期内，我们的目标是将其转化为真正的催化作用。如果成功，这将为主题 1 带来新的、更清洁的选择来创建碳骨架，即有机化合物（包括药物）的主干。在主题 2 中，催化的成功将使人们能够更容易、更清洁地获得一系列有机硅化合物，这些化合物可用于有机合成以及材料制备。