Organometallic and Coordination Chemistry Approaches to Small Molecule Activation Relevant to Renewable Energy and Resources

本课程的重点是通过探索二氧化碳的有机金属化学，从二氧化碳中提取有机燃料和化学品的分子方法。尽管二氧化碳因其稳定性和作为温室气体的作用而臭名昭著，但它也是廉价、丰富、无毒和可再生的。开发有效的方法将这种丰富的碳源转化为有用的材料，可以形成一个新的、可持续的化学工业和能源经济的基础，可以与基于不可再生化石资源的石化行业相媲美。我的计划的目标是设计能够通过为二氧化碳的功能化提供更低的能量途径来催化二氧化碳转化的络合物。为了降低实施成本，拟议的系统基于丰富的金属，并使用分子支架或配体，以使这些廉价的金属模仿更贵重的金属的反应性。这些系统从自然界用来执行类似挑战的转化的分子机械中获得灵感，使催化剂的多个部分能够与底物反应。在一种情况下，将建立能够结合两个性质非常不同的金属离子的配体，以测试第二种金属对第一种金属的电子和化学性质的影响。对这种合作的系统研究是开发新型催化剂的关键，这种催化剂的目标是进行涉及电子转移的二氧化碳转化。在第二条脉络中，将寻求利用廉价的过渡金属中心促进二氧化碳和其他小分子的偶联反应催化的配体，以将二氧化碳纳入广泛使用的商品化学品。由于这些类型的催化转化对廉价金属具有挑战性，利用配体支架的积极参与的基础洞察力将扩大使用丰富材料进行贵金属类型反应的可能场景。除了开发建立我们的目标系统所需的合成化学外，这项研究还旨在更好地了解它们的使用中涉及的新的反应机理。这些基础研究将导致更多活性和选择性的催化剂，并将其推广到其他化学应用。因此，该计划中提出的研究有望对环境和工业产生重大影响，同时为化学家的工具箱增加创新的新反应途径。参与这一研究项目的学生将拥有独特的技能和装备，拥有与行业相关的知识基础和创造力，这对加拿大快速增长的绿色能源和可再生资源部门来说是非常可取的。

This program focuses on molecular approaches to deriving organic fuels and chemicals from carbon dioxide through exploring its organometallic chemistry. While infamous for both its stability and its role as a greenhouse gas, carbon dioxide is also cheap, abundant, non-toxic and renewable. Developing efficient methods to convert this plentiful source of carbon into useful materials could form the basis of a new, sustainable chemical industry and energy economy that would rival a petrochemical one based on non-renewable fossil sources. The goal of my program is to design complexes that can catalyze transformations of carbon dioxide by providing lower energy pathways to its functionalization. To reduce the cost of implementation, the proposed systems are based on abundant metals and use molecular scaffolds, or ligands, to get these inexpensive metals to mimic the reactivity of their more precious counterparts. These systems draw inspiration from the molecular machinery nature uses to perform similarly challenging transformations by enabling multiple parts of a catalyst to cooperate in reacting with a substrate. In one context, ligands that can bind two metal ions of very different character will be built to test the influence of the second metal on the electronic and chemical properties of the first one. Systematic studies of this sort of cooperation are key for the development of novel catalysts targeted to carry out transformations of carbon dioxide that involve electron transfer. In a second vein, ligands that can facilitate the catalysis of coupling reactions of carbon dioxide and other small molecules using inexpensive transition metal centres will be pursued to incorporate carbon dioxide into widely used commodity chemicals. As these types of catalytic transformations are challenging for inexpensive metals, fundamental insight into exploiting the active participation of ligand scaffolds will expand the possible scenarios for precious-metal-type reactivity using abundant materials. In addition to developing the synthetic chemistry required to build our target systems, this research also aims to better our understanding of the novel reaction mechanisms involved in their use. These fundamental studies will lead to more active and selective generations of catalysts, and spread their deployment to other chemical applications. The research proposed in this program therefore holds promise of both significant environmental and industrial impact, while adding innovative new reaction pathways to the chemist’s toolbox. Students participating in this research program will emerge uniquely skilled and equipped with an industrially relevant knowledge base and a sense of creativity that should be highly desirable to Canada’s rapidly growing green energy and renewable resource sectors.