CAS: Catalysis with Cobalt Hydrides

在化学系化学催化项目的支持下，辛辛那提大学关海荣教授和他的团队将研究钴氢化物的催化活性。催化在医药、能源和材料的化学合成中起着不可缺少的作用。贵金属通常是设计催化剂的首选金属。然而，它们价格昂贵，供应有限，有时难以从产品中去除。在这个项目中，关博士将专注于钴这种廉价且地球上储量丰富的金属，研究带有钴-氢键的分子的反应性，钴-氢键是许多钴催化反应的关键中间体，但人们对钴-氢键知之甚少。通过这个项目，关博士和他的团队将积极参与外展和培训活动，使来自代表性不足群体的学生受益，包括那些参加辛辛那提大学科学和工程本科生研究项目和ACS项目SEED项目的学生，以及主要与本科院校合作的学生。关博士还将开发以研究为基础的课程材料和光谱资源，以期提高教育经验。在这个项目中，关海荣教授和他的研究团队旨在了解不同的配体平台如何影响钴氢化物的反应性。本课题将重点阐明单膦稳定的氢化钴配合物催化硅氢化、硼氢化和氢磷化反应的机理细节，并探索由螯合的氢化钴催化的新反应。还将调查pi-烯丙基和羟基环戊二烯基钴配合物如何在氢转移反应中作为掩面氢化物，以及作为减少二氧化碳和氯化和氟化化合物脱卤的电催化剂。所提出的研究有望为钴氢化物催化的基础知识做出贡献。在这些研究中获得的经验教训有可能在地球丰富过渡金属催化的更大领域产生广泛的科学影响。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Catalysis Program of the Division of Chemistry, Professor Hairong Guan and his group at the University of Cincinnati will examine the catalytic activities of cobalt hydrides. Catalysis plays an indispensable role in chemical synthesis for pharmaceutical, energy, and materials applications. Precious metals are often the metals of choice for designing catalysts. However, they are expensive, limited in supply, and sometimes difficult to remove from the products. In this project, Dr. Guan will focus on cobalt, an inexpensive and earth-abundant metal, to study the reactivity of molecules bearing cobalt-hydrogen bonds, which are poorly understood, but are key intermediates in many cobalt-catalyzed reactions. Through this project, Dr. Guan and his team will be actively engaged in outreach and training activities that benefit students from underrepresented groups, including those participating in the Undergraduates Pursuing Research in Science and Engineering Program at the University of Cincinnati and the ACS Project SEED Program as well as from collaborating predominantly undergraduate institutions. Dr. Guan will also develop research-based course materials and spectral resources that are expected to enhance the educational experience.In this project, Professor Hairong Guan and his research team aim to develop an understanding of how different ligand platforms impact the reactivity of cobalt hydrides. This research project will focus on elucidating the mechanistic details of hydrosilylation, hydroboration, and hydrophosphination reactions catalyzed by monophosphine-stabilized cobalt hydride complexes, and explore new reactions catalyzed by pincer-ligated cobalt hydrides. Also under investigation will be how pi-allyl and hydroxycyclopentadienyl cobalt complexes behave as masked hydrides in hydrogen transfer reactions as well as electrocatalysts for the reduction of carbon dioxide and the dehalogenation of chlorinated and fluorinated compounds. The proposed research studies are expected to contribute to the foundational knowledge of cobalt hydrides in catalysis. The lessons learned in these studies have the potential for broad scientific impact in the larger field of earth abundant transition metal catalysis.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.