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: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=716135
• 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。这些方向集中于实现能源和环境相关目标的光催化和电催化方法。该提案解决了与催化剂开发相结合的化学设计的基本方面，并形成了独特的计划和卓越的培训环境。具体来说，该提案提出了三个完全整合的研究主题。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常规金属-配体键合相互作用、不寻常的金属配位几何形状以及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重视。我们的策略利用具有受限几何特征的配体，这些特征决定了它们的键合轨道的排列。由此产生的配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。这些计划采用了几个配体家族，这些配体将用于催化流中的发现。 第二个研究方向侧重于电催化路线，用于还原二氧化碳以产生 C1 产品以及从中性水中产生氢气。二氧化碳的转化提供了将这种普遍存在的燃烧副产品回收成含能产品的潜力。这方面的成功将导致范式转变，将二氧化碳视为原料而不是废物。从水中制取氢气的电催化路线提供了一种清洁的可再生燃料，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。该提案提出了使用第一个研究主题中设计的复合体的几条研究方向。我们的重点是地球上丰富的金属配合物，涉及金属中心的变化以及配体修饰的目标位点。 光可以为催化提供替代能源，而产生氢气和转化/还原二氧化碳的均相光催化路线是我们项目第三个主题的核心。同样，重点是来自第一个研究流的地球丰富的金属配合物。计划将包括针对特定的修饰位点，这将调节催化金属中心的电子供给和支架的π共轭。 我们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，从而形成正反馈循环，这不仅会提高活性，而且还会导致全新催化剂的发现。总的来说，我们的方法计划消除该领域的一些偶然特征。