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

该计划的重点是通过探索其有机金属化学从二氧化碳中获得有机燃料和化学品的分子方法。虽然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，可以形成新的可持续化学工业和能源经济的基础，与基于不可再生化石资源的石化工业相媲美。我的计划的目标是设计复合物，可以通过提供较低的能量途径来催化二氧化碳的转化。为了降低实施成本，所提出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拟其更贵重的对应物的反应性。这些系统从分子机械中汲取灵感，通过使催化剂的多个部分在与底物反应中合作来执行类似的具有挑战性的转化。在一种情况下，可以结合两种性质非常不同的金属离子的配体将被构建，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，这些催化剂旨在进行涉及电子转移的二氧化碳转化。在第二方面，将寻求能够促进使用廉价的过渡金属中心催化二氧化碳和其他小分子的偶联反应的配体，以将二氧化碳掺入广泛使用的商品化学品中。由于这些类型的催化转化对廉价金属具有挑战性，对利用配体支架的积极参与的基本见解将扩大使用丰富材料的贵金属型反应性的可能方案。除了开发构建我们的目标系统所需的合成化学之外，这项研究还旨在更好地理解其使用中涉及的新型反应机制。这些基础研究将导致更活跃和选择性的催化剂，并将其应用推广到其他化学应用。因此，该计划中提出的研究有望产生重大的环境和工业影响，同时为化学家的工具箱增加创新的新反应途径。参加这项研究计划的学生将出现独特的技能，并配备了工业相关的知识基础和创造力，应该是非常可取的加拿大快速增长的绿色能源和可再生资源部门的意识。

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.