Small Molecule Activation and Homogeneous Catalysis with Organometallic Molecules Based on Sustainable Transition Metals

基于可持续过渡金属的有机金属分子小分子活化和均相催化

• 批准号: RGPIN-2018-03693
• 负责人: Piers, Warren
• 金额: $ 15.3万
• 依托单位: University of Calgary
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748049
• 关键词: Small; Molecule; Activation; Homogeneous; Catalysis

The catalysis of chemical transformations is the cornerstone of the chemical industry's major contribution to modern society. Catalystschemical entities that increase the rate and selectivity of a transformation without being used up in the processare needed for the manufacture of the vast majority of chemical products. Innovation in catalysis has thus been a key contributor to the high standard of living enjoyed by Canadians. Developments in catalysis are also essential for the future of human society. The significant energy and environmental challenges humanity faces will be surmounted primarily through technological advances in catalysis. Specifically, the selective and rapid catalysis of reactions that are energetically unfavorable remains a challenge for the field. Most important among such reactions involve the activation and conversion of the small molecules that are the end products of combustion (H2O, CO2) or the nitrogen cycle (N2). Conversion of by-products and pollutants derived from these processes (CH4, N2O) is also of prime interest. The discovery of molecular catalysts based on transition metals that are capable of converting these and other small molecules into useful products such as fuels or value added chemicals is an overarching objective of this research program. Since carrying out these reactions at the large scale necessary to have an impact in solving environmental and energy problems, a second objective is to develop catalysts that utilize the earth abundant metals like iron, nickel and cobalt.As synthetic chemists, our group's approach is to design and synthesize new ligands for transition metal (TM) complexes that will be active catalysts for such transformations. A “ligand” is an organic molecule that binds to the TM and both shapes the space around the metal and tunes its ability to bind and activate small molecules. Desirable ligand design features include the following: multidenticity (3-5 points of contact with the central metal), electron richness to encourage formation of high oxidation state intermediates, pi conjugation to allow for the management of electrons in multielectron reactions, and acid and base sites proximal to the central TM to allow for the management of protons. We create ligands with a combination of these features and then explore their coordination chemistry on TMs and evaluate the performance of these compounds as catalysts for the above mentioned reactions.The proposal describes our group's specific scientific approach, which focuses on 2 recently developed families of ligands with the above features, as well as exciting new ligand designs for novel TM coordination environments and catalysis.A team of 8-10 researchers, led by Dr. Warren Piers, will explore these important questions, gaining technical expertise, communication skills and problem solving abilities that equip them to be innovators of tomorrow.

化学转化的催化是化学工业对现代社会的主要贡献的基石。催化剂实体会提高转化的速率和选择性，而无需在制造绝大多数化学产品的过程中所需的过程中使用。因此，催化中的创新是加拿大人享有的高级生活水平的关键因素。催化中的发展对于人类社会的未来也是必不可少的。人类面临的重大能源和环境挑战将主要通过催化技术进步来克服。具体而言，基本不利的反应的选择性和快速催化仍然是该领域的挑战。在此类反应中，最重要的是小分子的激活和转化是组合的最终产物（H2O，CO2）或氮循环（N2）。从这些过程（CH4，N2O）得出的副产品和污染物的转化也是主要的关注。基于过渡金属的分子催化剂的发现，这些金属能够将这些和其他小分子转化为有用的产品，例如燃料或增值化学物质，是该研究计划的总体目标。由于对解决环境和能源问题产生影响的大规模进行这些反应，因此第二个目标是开发利用地球丰富的金属等催化剂，例如综合化学家，我们小组的方法是将新的配体定义和合成用于过渡金属（TM）复合物的新配体，以使其具有活跃的猫科动物的转型。 “配体”是一种有机分子，它与TM结合并塑造了金属周围的空间，并调节其结合和激活小分子的能力。理想的配体设计特征包括以下内容：多身份（与中央金属的3-5点接触），电子丰富度，以鼓励形成高氧化状态中间体，PI结合以在多电体反应中管理电子，以及与中央TM近端的酸和基础位置，以便允许蛋白质的管理。 We create ligands with a combination of these features and then explore their coordination chemistry on TMs and evaluate the performance of these compounds as catalysts for the above mentioned reactions.The proposal describes our group's specific scientific approach, which focuses on 2 recently developed families of ligands with the above features, as well as exciting new ligand designs for novel TM coordination environments and catalysis.A team of 8-10 researchers, led by Dr. Warren码头将探索这些重要问题，获得技术专长，沟通技巧和解决问题的能力，使他们成为明天的创新者。