Dynamical Organometallic Mechanisms

动态有机金属机制

基本信息

批准号：
1952420
负责人：
Daniel Ess
金额：
$ 26.53万
依托单位：
Brigham Young University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-09-01 至 2023-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1952420&HistoricalAwards=false
关键词：
Dynamical Organometallic Mechanisms

项目摘要

In this project, funded by the Chemical Structure, Dynamics, and Mechanisms B Program of the Chemistry Division, Professor Daniel Ess of the Department of Chemistry and Biochemistry at Brigham Young University is developing new experimentally testable theories about how the dynamic motion of atoms during the course of chemical reactions impacts how the reactions occur (reaction mechanisms). The goal of this research is to use the combination of a quantum mechanical treatment of the energy and forces with classical mechanical equations of motion to discover new reaction pathways and mechanisms for organometallic reactions. Quantum mechanics deals with the mathematical description of the motion and interaction of subatomic particles, incorporating the concepts of quantization of energy, wave-particle duality, and the uncertainty of how fast a tiny particle moves and how well we know its position. Classical mechanical describes the motion of macroscopic objects, from projectiles to parts of machinery, and astronomical objects, such as spacecraft, planets, stars and galaxies. This project combines the use of equations of physics, at both the atomic and macroscopic scales. The research project is a fruitful training ground to prepare undergraduate and graduate students for the scientific workforce. Undergraduate students will learn computational techniques that will be valuable in their future experimental careers. In addition to mentoring physical science students, this work provide cross disciplinary training in computer science.This work uses quasiclassical direct molecular dynamics trajectories to discover new dynamical organometallic reaction mechanisms, and examine major concepts that provide understanding and prediction of dynamical mechanisms. Many organometallic reactions involve highly reactive or weakly coordinated intermediates and their calculated energy landscapes provide an incomplete mechanistic picture. Quasiclassical direct molecular dynamics trajectories reveal new dynamical mechanisms. In this project, the focus is on direct dynamics studies of experimentally important alkane, arene, and alkene oxidative additions and reductive elimination reactions, which represent one of the largest and most important classes of organometallic 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.

在该项目中，由化学部门的化学结构，动力学和机制B计划资助，化学和生物化学系的丹尼尔·埃斯（Daniel Ess）教授正在开发有关化学反应过程中原子动态运动如何影响反应的新实验测试理论（反应机制）。这项研究的目的是将能量和力与经典运动方程的量子机械处理结合使用，以发现有机金属反应的新反应途径和机制。量子力学涉及亚原子粒子运动和相互作用的数学描述，结合了能量量化，波颗粒对偶性的概念，以及微小粒子移动的速度以及我们如何了解其位置的不确定性。古典机械描述了宏观物体的运动，从弹丸到机械的部分以及天文对象，例如航天器，行星，恒星和星系。该项目结合了原子和宏观尺度上物理方程的使用。该研究项目是一个富有成果的培训场所，为科学劳动力做准备本科生和研究生。本科生将学习在未来的实验职业中有价值的计算技术。除了指导物理科学专业的学生外，这项工作还提供了计算机科学中的跨学科培训。这项工作使用了准经典直接分子动力学轨迹来发现新的动力学有机金属反应机制，并研究了提供对动力学机制的理解和预测的主要概念。许多有机金属反应涉及高反应性或弱协调的中间体，其计算出的能量景观提供了不完整的机械图。准经典直接分子动力学轨迹揭示了新的动力学机制。在该项目中，重点是对实验重要的烷烃，Arene和烯烃氧化的添加和还原性消除反应的直接动态研究，这代表了最大，最重要的有机金属反应类别之一。这奖反映了NSF的法规任务，并被认为是通过基金会的知识优点和广泛的范围来评估的，并且值得通过评估来进行评估。

项目成果

期刊论文数量（11）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Catalysis with a Skip: Dynamically Coupled Addition, Proton Transfer, and Elimination during Au- and Pd-Catalyzed Diol Cyclizations

跳过催化：金和钯催化二醇环化过程中的动态耦合加成、质子转移和消除

DOI：
10.1021/acscatal.1c02408
发表时间：
2021
期刊：
ACS Catalysis
影响因子：
12.9
作者：
Teynor, Matthew S.;Scott, Windsor;Ess, Daniel H.
通讯作者：
Ess, Daniel H.

Direct Dynamics Trajectories Demonstrate Dynamic Matching and Nonstatistical Radical Pair Intermediates during Fe-Oxo-Mediated C–H Functionalization Reactions

直接动力学轨迹展示了 Fe-Oxo 介导的 C–H 功能化反应过程中的动态匹配和非统计自由基对中间体

DOI：
10.1021/jacs.3c01196
发表时间：
2023
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Joy, Jyothish;Ess, Daniel H.
通讯作者：
Ess, Daniel H.

Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes

探索古巴烷作为潜在苯等排体和含能材料：古巴烷区域选择性重排的范围和机制研究

DOI：
10.1021/jacs.3c03226
发表时间：
2023
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Son, Jeong-Yu;Aikonen, Santeri;Morgan, Nathan;Harmata, Alexander S.;Sabatini, Jesse J.;Sausa, Rosario C.;Byrd, Edward F.;Ess, Daniel H.;Paton, Robert S.;Stephenson, Corey R.
通讯作者：
Stephenson, Corey R.

Mechanistic molecular motion of transition-metal mediated β-hydrogen transfer: quasiclassical trajectories reveal dynamically ballistic, dynamically unrelaxed, two step, and concerted mechanisms

过渡金属介导的β-氢转移的机械分子运动：准经典轨迹揭示动态弹道、动态非松弛、两步和协同机制