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3年里，我们的研究计划，目标和培训环境进行了广泛的重新定义。这些方向集中在光催化和电催化方法的能源和环境相关的目标。该提案涉及化学设计的基本方面，与催化剂开发相一致，并为独特的计划和良好的培训环境做出了贡献。具体而言，该提案提出了三个完全综合的研究主题。第一个建立在我们的开创性，基本目标，设计和组装分子支架与非常规的金属配体键合相互作用，不寻常的金属配位几何形状，和定制的电子各向异性的配位金属。这些重要的基本相互作用的影响最近在我们的贡献者的文献中得到了赞赏。我们的策略利用配体的限制几何特征，决定其键合轨道的对齐。复合物的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家庭的配体，将被应用于发现的催化流。 第二个研究流侧重于电催化途径，用于还原CO2以产生C1产品和从中性水中产生H2。CO2的转化提供了将这种无处不在的燃烧副产物再循环成含能量产品的潜力。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。从水到H2的电催化路线提供了一种清洁和可再生的燃料，具有巨大的潜力来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复合物的几条研究路线。我们的重点是地球上丰富的金属配合物，并涉及金属中心的变化，以及配体修饰的目标网站。 光可以为催化提供替代能源，H2生成和CO2转化/还原的均相光催化途径是我们计划的第三个主题的核心。同样，重点是地球丰富的金属络合物，将来自第一个研究流。计划将包括靶向特定的修饰位点，这将调节电子捐赠到催化金属中心和支架的π共轭。 我们的两个基于催化的主题的结果将用于指导复杂的设计和合成，从而形成正反馈循环，这不仅会提高活性，还会导致发现全新的催化剂。总的来说，我们的方法计划删除这个字段的一些偶然发现的功能。