Dynamics of Organometallic Reaction Mechanisms

杨百翰大学化学系和生物化学系的Daniel Ess教授在化学系化学结构、动力学和机理B项目的支持下，正在研究分子内原子的运动如何决定复杂有机金属反应的机理和选择性的新基础理论。本研究的目标是结合能量和力的量子力学方法、经典力学运动方程和复杂的溶剂处理，发现有机金属反应的新途径和机制。这项研究可能会显著改变对有机金属反应的基本理解、解释和设计，有机金属反应是最重要的化学反应之一。该项目结合了计算化学、无机化学、有机化学和计算机科学，是为科学工作者准备本科生和研究生的多样化训练基地。本项目利用准经典的直接密度泛函理论、分子动力学轨迹来发现有机金属反应的机制和选择性的新基本原理，有机金属反应是化学中最重要的反应类别之一。本研究的重点是具有紧密电子自旋态的有机金属反应和轨迹中可能的自旋交叉。此外，这项工作的重点是开发和应用复杂的方案，模拟显式溶剂在有机金属反应轨迹。正在研究的有机金属反应包括自由基环化反应、键活化反应和金属氧反应。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 of the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Daniel Ess of the Department of Chemistry and Biochemistry at Brigham Young University is developing new foundational theories about how the motion of atoms within molecules determines the mechanisms and selectivity during complex organometallic reactions. The goal of this research is to combine quantum mechanical methods for energy and forces, classical mechanical equations of motion, and sophisticated treatment of solvent to discover new reaction pathways and mechanisms for organometallic reactions. This research could significantly alter the fundamental understanding, interpretation, and design of organometallic reactions, one of the most important classes of chemical reactions. This project combines computational chemistry, inorganic chemistry, organic chemistry, and computer science, and is a diverse training ground to prepare undergraduate and graduate students for the scientific workforce.This project uses quasiclassical direct density functional theory, molecular dynamics trajectories to discover new fundamental principles of mechanisms and selectivity for organometallic reactions, which are one of the most important reaction classes in chemistry. This work focuses on organometallic reactions with close electronic spin states and possible spin crossover during trajectories. Additionally, this work focuses on developing and applying sophisticated protocols for modeling explicit solvent during organometallic reaction trajectories. Organometallic reactions that are being examined include radical cyclization reactions, bond activation reactions, and metal oxo reactions.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.