Organo-f element Chemistry: Integrated Synthetic, Mechanistic, and Catalytic and Thermochemical Studies

通过该奖项，化学部的化学催化项目资助西北大学的Tobin Marks博士发现、理解和优化涉及金属催化剂的化学转化。这些过程对化工企业至关重要，包括生产燃料、塑料、药品和其他经济上重要的化学品的高效、原子经济和可持续的催化过程。该项目涉及四个相互关联的重点领域，将研究和教育相结合，并处理利用地球丰富的金属催化剂的新型催化反应的基础和技术导向方面。计算分析被用来理解催化转化，最重要的是，发现新的催化转化。一个正在完成的平行目标是阐明新的、有效的、有用的、原子高效的和环境“绿色”催化过程的原理。参与这个多方面/多学科的项目，包括与工业科学家的互动，正在为具有不同背景的学生在工业、政府实验室和学术界的职业生涯做好准备。马克斯教授主要研究四个领域：1)催化氢元化，以发现、表征和理解介导杂元素氢添加到碳-碳饱和的原子效率过程。该项目专注于未开发的镧系催化过程，这些过程耦合多个催化成键事件（级联），利用不饱和杂环（脱芳化），发明形成氧-碳和硫-碳键的新方法，并提供锕系催化剂，介导新的成键序列。2)极性介质中的亲电催化：利用可回收的、高度亲电的镧系催化剂，在非挥发性的、可回收的离子液体或其他极性溶剂中，研究氢元化及其反过程，以实现新的氢元化过程，并开发催化反应，当与氢化耦合时，实现微观反：与氢裂解碳氧、碳氮和碳硫键。这项研究对更有效地处理可持续生物燃料和其他自然资源具有启示意义。3)催化材料合成利用镧系元素、锕系元素及相关过渡金属催化剂，研究烯烃聚合过程与氢元素的偶联，生成杂原子功能化聚合物，从而在聚合物链端引入极性官能团。4)多核催化：通过两个靠近的催化中心来改变催化聚合和共聚反应的过程。理想情况下，这种协同效应可能会改变控制聚合物结构、机械性能和加工特性的动力学事件的速率和选择性。

With this award, the Chemical Catalysis Program in the Chemistry Division is funding Dr. Tobin Marks of Northwestern University to discover, understand, and optimize chemical transformations involving metal catalysts. Such processes are of central importance to the chemical enterprise and include efficient, atom-economical, and sustainable catalytic processes for producing fuels, plastics, pharmaceuticals, and other economically important chemicals. This project involves four interlinked focus areas that integrate research and education, and deal with fundamental and technologically-oriented aspects of new catalytic reactions utilizing earth-abundant metal catalysts. Computational analysis is being used to understand the catalytic transformations, and most importantly, to discover new ones. A parallel goal being accomplished is the elucidation of principals for new, efficient, useful, atom-efficient, and environmentally "green" catalytic processes. Participation in this multifaceted/multidisciplinary project, including interactions with industrial scientists, is preparing students with diverse backgrounds for careers in industry, government laboratories, and academia. Professor Marks is studying four research areas: 1) Catalytic hydroelementation to discover, characterize, and understand atom-efficient processes that mediate heteroelement-hydrogen additions to carbon-carbon saturation. This project is focusing on unexplored, lanthanide-catalyzed processes that couple multiple catalytic bond-forming events (cascades), that utilize unsaturated heterocycles (dearomatization), that invent new ways to form oxygen-carbon and sulfur-carbon bonds, and provide actinide catalysts which mediate new bond-forming sequences. 2) Electrophilic catalysis in polar media to study hydroelementation and its reverse using recyclable, highly electrophilic lanthanide catalysts in non-volatile, recyclable ionic liquids or other polar solvents to effect new hydroelementation processes and to develop catalytic reactions that, when coupled to hydrogenation, achieve the microscopic reverse: cleaving carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds with hydrogen. This research has implications for more efficient processing of sustainable biofuels and other natural resources. 3) Catalytic materials synthesis to use lanthanide, actinide, and related transition metal catalysts in investigating the coupling of olefin polymerization processes with hydroelementation, to produce heteroatom-functionalized polymers, thereby introducing polar functionality at polymer chain ends. 4) Multinuclear catalysis to alter the course of catalytic polymerization and copolymerization reactions by poising two catalytic centers in close proximity. Ideally, such cooperativity effects are likely to alter both the rates and selectivities of kinetic events that control polymer architecture, mechanical properties, and processing characteristics.