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，我们对研究项目、目标和培训环境进行了广泛的重新定义。这些方向以光催化和电催化方法为中心，以实现能源和环境相关目标。该方案解决了与催化剂开发相一致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。具体而言，该提案提出了三个完全整合的研究主题。第一个是基于我们开创性的基本目标，设计和组装具有非常规金属-配体键相互作用的分子支架，不寻常的金属配位几何形状，以及协调金属的定制电子各向异性。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。我们的策略是利用具有限制几何特征的配体，这些特征决定了它们成键轨道的排列。配合物的物理和化学性质的变化将支持另外两个主题，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家族的配体，将用于发现催化流。