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，特别是对于许多经典的单金属策略尚未解决的具有挑战性的化学反应。目前，科学家们还不完全了解双核催化剂是如何工作的，或者如何改进它们。在这个项目中，杨百翰大学的丹尼尔埃斯博士正在使用计算方法来理解双核金属-金属相互作用的机制和发展的一般原则。这项工作与实验合作紧密结合，导致了新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了化学和计算机科学接口的科学培训。Ess博士参与了与本研究相关的几项推广活动。例如，Ess博士每年都会在杨百翰大学为100多名9-14岁的儿童和青少年主持一个夏季化学夏令营，其中有大量来自代表性不足的群体的参与。在化学部化学催化计划的资助下，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。正在研究的催化剂在两种过渡金属之间或过渡金属和主族金属之间具有单个共价键或直接的配位/静电相互作用。正在研究用于反应如碳-碳偶联、炔氢化和芳烃胺化的钴-锆、铼-银、二镍和二铑催化剂的反应机理。双核催化剂的反应性和选择性的原理正在开发通过比较双核与单核催化剂，以及金属-金属配对的影响，用于反应，如乙烯聚合和二烯加氢芳基化的铑-锆，铑-银，铑-锂和镍-钠催化剂。本工作还利用计算方法设计了用于芳烃硼化和手性烯丙基胺化的新型异双核催化剂。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软件。学生与实验小组互动，并学习如何将计算化学与实验相结合。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化学和生物化学夏令营，参与人数众多。该奖项反映了NSF的法定使命，并通过使用基金会的智力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.