From Fundamental Investigations to Catalysis: New Motifs in Main Group and Transition Metal Complexes

从基础研究到催化：主族和过渡金属配合物的新基序

• 批准号: RGPIN-2019-07235
• 负责人: Richeson, Darrin
• 金额: $ 2.11万
• 依托单位: University of Ottawa
• 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=748201
• 关键词: Fundamental; Investigations; Catalysis; New; Motifs

The last 3 years have seen an extensive redefinition of our research program, goals and training environment. These directions center on photocatalytic and electrocatalytic approaches to energy and environmentally relevant targets. This proposal addresses fundamental aspects of chemical design in concert with catalyst development and makes for a unique program and excellent training environment. Specifically, the proposal presents three fully integrated research themes. The first builds on our pioneering, fundamental objective to design and assemble molecular scaffolds with unconventional metal-ligand bonding interactions, unusual metal coordination geometries, and tailored electronic anisotropy of the coordinated metal. The impact of these important fundamental interactions has recently been appreciated in the literature to which we contributors. Our strategy exploits ligands with restricted geometric features that dictate the alignment of their bonding orbitals. The resulting changes to physical and chemical properties of the complexes will support the other two themes and lead to unprecedented reactivity and catalysis. These plans employ several families of ligands that will be applied for discovery in the catalysis streams. The second research stream focuses on electrocatalytic routes for reduction of CO2 to yield C1 products and the generation of H2 from neutral water. The transformation of CO2 provides the potential to recycle this ubiquitous combustion by-product into energy containing products. Success here will result in a paradigm shift to viewing CO2 as a feedstock rather than as a waste product. Electrocatalytic routes to H2 from water provide a clean and renewable fuel with enormous potential to address the world's energy demands while simultaneously fulfilling a mandate for environmental stewardship. The proposal presents several lines of research that use the complexes designed in the first research theme. Our focus is on earth-abundant metal complexes and involves variation of the metal center as well as targeted sites of ligand modification. Light can provide an alternative energy source for catalysis and homogeneous photocatalytic routes to H2 generation and transformation/reduction of CO2 are core to the third theme of our program. Again, the focus is on earth-abundant metal complexes that will be derived from the first research stream. Plans will include targeting specific sites of modification, which will modulate the electron donation to the catalytic metal center and the pi-conjugation of scaffold. The results from our two catalysis-based themes will be used to dictate complex design and synthesis leading to a positive feedback loop that will not only improve activity but will also lead to discovery of entirely new catalysts. Overall, our approach plans to remove some of the serendipitous features of this field.

在过去的三年中，我们的研究计划，目标和培训环境有了广泛的重新定义。这些方向集中在能量和环境相关靶标的光催化和电催化方法上。该提案涉及与催化剂开发协同化学设计的基本方面，并为独特的计划和出色的培训环境提供了。具体而言，该提案提出了三个完全集成的研究主题。第一个建立在我们的开创性，基本目标上，以设计和组装分子支架，具有非常规金属配体键相互作用，异常的金属协调几何形状以及协调金属的电子各向异性。这些重要的基本互动的影响最近在我们贡献者的文献中得到了赞赏。我们的策略以有限的几何特征利用配体，以决定其粘结轨道的对齐。配合物的物理和化学特性的结果变化将支持其他两个主题，并导致前所未有的反应性和催化。这些计划雇用了几个配体家庭，这些家族将在催化流中进行发现。 第二个研究流着重于减少CO2的电催化途径，从而产生C1产物和中性水的H2产生。 CO2的转化提供了将这种无处不在的燃烧副产品回收为含有产物的能量的潜力。这里的成功将导致将CO2视为原料而不是废产品的范式转移。从水到H2的电催化路线提供了一种清洁，可再生的燃料，具有巨大的潜力，可以满足世界能源需求，同时履行环境管理的任务。该提案提出了几条研究线，使用了第一个研究主题中设计的复合物。我们的重点是土壤丰富的金属络合物，涉及金属中心的变化以及配体修饰的靶向位点。 光可以为H2生成和转化/减少CO2提供催化和同质光催化途径的替代能源，这是我们计划的第三个主题的核心。同样，重点是将源自第一个研究流的地球丰富的金属络合物。计划将包括针对特定的修改部位，该位点将调节对催化金属中心的电子捐赠和支架的PI缀合。我们两个基于催化的主题的结果将用于决定复杂的设计和合成，从而导致积极的反馈回路，这不仅会改善活动，而且还将导致发现全新的催化剂。总体而言，我们的方法计划删除该领域的一些偶然功能。