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重大贡献的基石，绝大多数化学产品的制造都需要能够提高转化速率和选择性且不会在过程中耗尽的催化剂化学实体。因此，催化技术是加拿大人享受高生活水平的关键因素。催化技术的发展对于人类社会的未来也至关重要，人类面临的重大能源和环境挑战将主要通过技术进步来克服。具体而言，对能量不利的反应的选择性和快速催化仍然是该领域的一个挑战，其中最重要的是燃烧最终产物（H2O、CO2）或小分子的活化和转化。氮循环（N2）。这些过程中产生的副产品和污染物（CH4、N2O）的转化也是人们最感兴趣的。基于过渡金属的分子催化剂的发现能够将这些和其他物质转化。将小分子转化为燃料或增值化学品等有用产品是该研究计划的首要目标，因为大规模进行这些反应对于解决环境和能源问题有必要，因此第二个目标是开发能够产生影响的催化剂。利用地球上丰富的金属，如铁、镍和钴。作为合成化学家，我们小组的方法是设计和合成过渡金属（TM）配合物的新配体，这些配体将成为此类转化的活性催化剂。“配体”是一种有机物。与 TM 结合的分子，既塑造金属周围的空间，又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：多齿性（与中心金属有 3-5 个接触点）、电子丰富度。促进高氧化态中间体的形成，π共轭以允许在多电子反应中管理电子，以及靠近中心TM的酸和碱位点以允许管理质子。结合这些特征，然后探索它们在 TM 上的配位化学，并评估这些化合物作为上述反应催化剂的性能。该提案描述了我们小组的具体科学方法，重点关注 2 个最近开发的具有上述特征的配体家族以及用于新颖 TM 配位环境和催化的令人兴奋的新配体设计。由 Warren Piers 博士领导的由 8-10 名研究人员组成的团队将探索这些重要问题，获得使他们具备的技术专业知识、沟通技巧和解决问题的能力成为创新者明天的。