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: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=739375
• 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.

在过去的三年里，我们对研究计划、目标和培训环境进行了广泛的重新定义。这些方向的重点是以光催化和电催化方法实现与能源和环境有关的目标。这项建议涉及与催化剂开发相协调的化学设计的基本方面，并创造了一个独特的计划和良好的培训环境。具体地说，该提案提出了三个完全综合的研究主题。第一个建立在我们开创性的基本目标之上，即设计和组装具有非传统金属-配体键合作用、不寻常的金属配位几何结构和配位金属的定制电子各向异性的分子支架。这些重要的基本相互作用的影响最近在我们贡献的文献中得到了赞赏。我们的策略利用了具有受限几何特征的配体，这些几何特征决定了它们的成键轨道的排列。由此产生的络合物物理和化学性质的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作用。这些计划使用了几个配体家族，这些配体将被应用于催化流中的发现。第二个研究重点是电催化途径，用于将二氧化碳还原为氯化产物，以及从中性水中生成氢气。二氧化碳的转化提供了将这种无处不在的燃烧副产物回收为含能产品的潜力。这方面的成功将导致范式的转变，将二氧化碳视为一种原料，而不是废物。电催化从水中转化为氢气的方法提供了一种清洁和可再生的燃料，具有巨大的潜力，可以满足世界的能源需求，同时履行环境管理的任务。该提案提出了使用第一个研究主题中设计的综合体的几个研究方向。我们的重点是地球上丰富的金属络合物，涉及金属中心的变化以及配体修饰的靶点。光可以为催化提供替代能源，生成氢气和转化/还原二氧化碳的均相光催化途径是我们计划的第三个主题的核心。再一次，重点放在地球上丰富的金属络合物上，这些络合物将来自第一个研究流。计划将包括针对特定的修饰位置，这将调节对催化金属中心的电子给予和支架的圆周率共轭。我们的两个基于催化的主题的结果将用于指示复杂的设计和合成，从而形成一个正反馈循环，不仅将提高活性，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特征。