Theory and Design of Transition-Metal Heterodinuclear and Homodinuclear Catalytic Reactions

开发新的催化剂对于发现新的化学反应至关重要。传统上，分子催化剂使用一个金属原子。具有两个金属原子（双核）的催化剂在新的反应性方面具有重要的前景，特别是在许多具有挑战性的化学反应中，传统的单金属策略尚未解决。目前，科学家们并不完全了解双核催化剂是如何运作的，或者如何改进它们。在这个项目中，杨百翰大学的Daniel Ess博士正在使用计算方法来理解机制并发展双核金属-金属相互作用的一般原理。这项工作与实验合作紧密结合，正在导致新的催化剂和化学反应的发现。这项工作还为研究生和本科生提供化学和计算机科学界面的科学训练。Ess博士参与了与这项研究相关的几项外展活动。例如，埃斯博士每年在杨百翰大学指导一个夏季化学夏令营，有100多名9-14岁的儿童和青少年参加，其中有很多来自代表性不足的群体。在化学部化学催化项目的资助下，杨百翰大学的Ess博士正在使用计算化学方法来发展对过渡金属异双核和同双核催化的理解。所研究的催化剂在两个过渡金属之间或过渡金属与主基团金属之间具有单一共价键或直接加法/静电相互作用。目前正在研究用于碳-碳偶联、炔加氢和芳烃胺化等反应的钴-锆、钌-银、镍和钯催化剂的反应机理。通过比较双核催化剂与单核催化剂的反应性和选择性原理，以及金属-金属配对对钌-锆、钌-银、铑-锂和镍-钠催化剂在乙烯聚合和二烯氢化反应中的影响，正在开发双核催化剂。本工作还利用计算方法设计了新的杂核催化剂，用于芳烃硼化和手性烯丙基胺化。本科生和研究生正在接受现代计算技术的培训，包括使用和开发自旋交叉反应和直接动力学的软件。学生与实验组互动，学习如何将计算化学与实验结合起来。Ess博士利用杨百翰大学的本科生实验室为100多名9-14岁的儿童和青少年举办了一个夏季化学和生物化学夏令营，其中有很多来自代表性不足的群体。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。

Developing new catalysts is essential to discovering new chemical reactions. Traditionally, molecular catalysts use one metal atom. Catalysts with two metal atoms (dinuclear) have significant promise for new reactivity, especially for many challenging chemical reactions not yet solved by the classic one metal strategy. Currently, scientists do not completely understand how dinuclear catalysts operate, or how they can be improved. In this project Dr. Daniel Ess of Brigham Young University is using computational methods to understand mechanisms and develop general principles of dinuclear metal-metal interactions. This work, combined tightly with experimental collaboration, is leading to the discovery of new catalysts and chemical reactions. This work also provides scientific training at the interface of chemistry and computer science for graduate and undergraduate students. Dr. Ess is engaged in several outreach activities related to this research. For example, each year Dr. Ess directs a summer chemistry camp at BYU for more than 100 children and youth ages 9-14 with significant participation from underrepresented groups.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Ess of Brigham Young University is using computational chemistry methods to develop understanding of transition-metal heterodinuclear and homodinuclear catalysis. Catalysts being investigated have a single covalent bond or direct dative/electrostatic interaction between two transition metals or a transition metal and main-group metal. Reaction mechanisms are being investigated for cobalt-zirconium, ruthenium-silver, dinickel, and dirhodium catalysts used in reactions such as carbon-carbon couplings, alkyne hydrogenation, and arene amination. Dinuclear catalyst principles of reactivity and selectivity are being developed by comparing dinuclear versus mononuclear catalysts, and the impact of metal-metal pairing, for ruthenium-zirconium, ruthenium-silver, rhodium-lithium, and nickel-sodium catalysts for reactions such as ethylene polymerization and diene hydroarylation. This work is also using computational methods to design new heterodinuclear catalysts for arene borylation and chiral allylic amination. Undergraduate and graduate students are being trained in modern computational techniques that include using and developing software for spin crossover reactions and direct dynamics. Students interact with experimental groups and are learning how to interface computational chemistry with experiment. Dr. Ess directs a summer chemistry and biochemistry camp using undergraduate labs at BYU for more than 100 children and youth ages 9-14 with significant participation from underrepresented groups.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.