Understanding the Reactions of Carbon Dioxide with Late Transition Metal Complexes

了解二氧化碳与后过渡金属配合物的反应

• 批准号: 1953708
• 负责人: Nilay Hazari
• 金额: $ 45万
• 依托单位: Yale 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: 2020-07-01 至 2024-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1953708&HistoricalAwards=false
• 关键词: Understanding; Reactions; Carbon; Dioxide; Late

The conversion of carbon dioxide (CO2) into more valuable compounds is an important goal due to the potential of this waste product as a readily available, sustainable, non-toxic, and inexpensive chemical feedstock. Catalysts based on transition metals, such as nickel or palladium, show promise speeding up the reactions of carbon dioxide so that they are practical, but improvements in efficiency are required for further implementation. In this project, Dr. Hazari of Yale University is developing an understanding of how carbon dioxide interacts with a variety of transition metal complexes using both experimental and computational techniques. This knowledge is crucial for the design of improved systems for carbon dioxide utilization as it will provide information on how to modify the catalyst as well as how to improve the conditions under which reactions are performed (temperature, pressure, etc.). This research has potential to increased selectivity so that only desired products are formed. The research is complemented by Dr. Hazari’s involvement in a series of outreach activities related to carbon dioxide utilization. These activities focus on students from underrepresented minorities in science, technology, engineering and mathematics (STEM) disciplines. The activities include a one week summer program on energy for high school students in the New Haven area and opportunities for undergraduates to perform research in Dr. Hazari’s laboratory. With funding from the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) Program of the Chemistry Division, Dr. Hazari from Yale University is developing a fundamental understanding of the insertion of carbon dioxide into late-transition metal bonds. This research provides guidance about the design of catalysts and optimization of reaction conditions for processes involving carbon dioxide utilization. Specifically, the rates of carbon dioxide insertion into Group 10 pincer-supported transition metal hydrides, hydroxides, alkyls, and aryls are being measured. Factors that are being probed include the effects of the metal center, ancillary ligand, solvent, and additives, such as Lewis acids, on the kinetics of carbon dioxide insertion. A major focus is the development of scaling relationships that correlate the rate of carbon dioxide insertion into a metal hydride (a kinetic property), with the hydricity of transition metal hydrides, a thermodynamic property. This enables the evaluation of hypotheses relating to whether secondary coordination sphere effects such as hydrogen bonding or electrostatic effects that stabilize the transition state for carbon dioxide insertion. Density Functional Theory calculations are carried out in parallel with the experimental work and probe the structure of the transition states, determine the geometries of unstable intermediates, and measure hydricity.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.

将二氧化碳 (CO2) 转化为更有价值的化合物是一个重要的目标，因为这种废物具有作为一种容易获得、可持续、无毒且廉价的基于过渡金属（如镍或镍）的化学原料的潜力。钯有望加速二氧化碳的反应，使其变得实用，但进一步实施需要提高效率。在这个项目中，耶鲁大学的哈扎里博士正在加深对二氧化碳如何与各种物质相互作用的理解。过渡金属这些知识对于设计改进的二氧化碳利用系统至关重要，因为它将提供有关如何修改催化剂以及如何改进反应进行条件（温度、压力）的信息。等）。这项研究有可能提高选择性，以便只形成所需的产品。哈扎里博士参与了一系列与二氧化碳利用相关的外展活动，这些活动重点关注来自代表性不足的少数族裔的学生。科学、技术、工程和这些活动包括为纽黑文地区的高中生提供为期一周的能源暑期课程，以及在化学结构、动力学和机理 B 的资助下为本科生在哈扎里博士的实验室进行研究的机会。 (CSDM-B) 耶鲁大学化学系项目的 Hazari 博士正在深入了解二氧化碳插入后过渡金属键的过程，这项研究为催化剂的设计和反应条件的优化提供了指导。具体来说，正在测量二氧化碳插入第 10 族钳形支撑过渡金属氢化物、氢氧化物、烷基和芳基化合物的速率。正在研究的因素包括金属中心、辅助配体的影响。 、溶剂和添加剂，如路易斯酸，对二氧化碳插入动力学的研究主要关注的是与二氧化碳插入金属氢化物的速率相关的比例关系的发展（动力学）。性质），以及过渡金属氢化物的水性（一种热力学性质），这使得能够评估与稳定二氧化碳插入过渡态的二次配位层效应（例如氢键）或静电效应有关的假设。与实验工作并行进行，探索过渡态的结构，确定不稳定中间体的几何形状，并测量水度。该奖项是 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。

项目成果

Ligand and solvent effects on CO 2 insertion into group 10 metal alkyl bonds

配体和溶剂对 CO 2 插入第 10 族金属烷基键的影响

• DOI: 10.1039/d1sc06346d
• 发表时间: 2022-02-23
• 期刊: Chemical Science
• 影响因子: 8.4
• 作者: Deziel AP;Espinosa MR;Pavlovic L;Charboneau DJ;Hazari N;Hopmann KH;Mercado BQ
• 通讯作者: Mercado BQ

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

氢化铼的热力学和动力学水度的相关性

• DOI: 10.1021/jacs.2c07192
• 发表时间: 2022-10
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Espinosa, Matthew R.;Ertem, Mehmed Z.;Barakat, Mariam;Bruch, Quinton J.;Deziel, Anthony P.;Elsby, Matthew R.;Hasanayn, Faraj;Hazari, Nilay;Miller, Alexander J.;Pecoraro, Matthew V.;et al
• 通讯作者: et al

Thermodynamic and kinetic hydricity of transition metal hydrides

过渡金属氢化物的热力学和动力学水度

• DOI: 10.1039/d0cs00405g
• 发表时间: 2020-11
• 期刊: Chemical Society Reviews
• 影响因子: 46.2
• 作者: Brereton, Kelsey R.;Smith, Nicholas E.;Hazari, Nilay;Miller, Alexander J.
• 通讯作者: Miller, Alexander J.