New Reaction Chemistry with Transition Metal Complexes for Conversion of Oxygenated

过渡金属配合物转化含氧化合物的新反应化学

• 批准号: 1800501
• 负责人: Theodor Agapie
• 金额: $ 45万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-15 至 2023-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800501&HistoricalAwards=false
• 关键词: New; Reaction; Chemistry; Transition; Metal

With funding from the Chemical Synthesis Program of the Division of Chemistry, Dr. Theodor Agapie of the California Institute of Technology is synthesizing molecular compounds to study the production of liquid fuels from carbon monoxide (CO) as a starting material. Liquid fuels (such as methanol and ethanol) are particularly desirable as they allow the U.S. economy to maintain its current energy infrastructure. While catalysts for the conversion of CO to fuels containing carbon-carbon bonds are known, their reactions are chemically challenging and poorly understood. Dr. Agapie's catalysts are capable of forming products containing the desirable carbon-carbon bonds using CO as a starting material. He is also using these compounds to systematically study the relationship between their structure and reactivity in order to develop a fundamental understanding of the principles controlling their behavior. Such advances help the US stay at the forefront of the energy economy. The Agapie group is involved in outreach activities with high school students in Pasadena, CA. They support the Caltech Classroom Connection, developing relationships with teachers as Marshall Fundamental High School. The visits by high school students and workshops on careers in science have engage students in STEM careers. Undergraduate students participate in the projects under Caltech programs Amgen and WAVE which have the goal of providing research opportunities to facilitate careers in science by students who are underrepresented in science. In addition to technical training, graduate students develop their mentorship skills by working with undergraduates, contributing to the education of a talented workforce. Dr. Agapie is systematically studying structure-reactivity relations of a family of molybdenum complexes in order to develop a fundamental understanding of the design principles controlling the selectivity of reductive coupling and deoxygenation of CO and CO2. Ligand architectures that display the ability to store electrons and change coordination modes are being prepared. Mechanistic and ligand design hypotheses are tested to determine the effect of the nature of donors, ligand lability, reduction potential, and electrophiles on the outcome of CO cleavage and coupling reactions. The use of mild reagents, which is necessary for practical applications, is targeted. Specific challenges that are being addressed include: 1) Determination of ligand effects on the cleavage of CO, to generate a metal carbide; 2) Determination of structural features controlling the extent of CO homologation (C2 vs C3, etc); 3) Determination of pathways for Cn (n greater than or equal to 2) product generation from observed intermediates using mild conditions (H+, H-, H2); 4) Evaluation of reagents that are relevant to practical applications such as protons as electrophiles, and hydride and H2 as sources of protons and electrons. These studies may provide the fundamental knowledge necessary for the design of inexpensive and practical catalysts for upgrading of carbon feedstocks to higher value chemicals and fuels. This project is being conducted by undergraduate and graduate students and is exposing them to several technical areas, including synthesis, spectroscopy, and mechanistic studies, all of which facilitate the development of a well-trained workforce.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.

在化学部化学合成计划的资助下，加州理工学院的Theodor Agapie博士正在合成分子化合物，以研究以一氧化碳(CO)为原料生产液体燃料。液体燃料(如甲醇和乙醇)特别受欢迎，因为它们使美国经济能够维持目前的能源基础设施。虽然已知用于将CO转化为含有碳-碳键的燃料的催化剂，但它们的反应在化学上具有挑战性，而且人们对其知之甚少。阿加皮博士的催化剂能够以一氧化碳为起始原料，形成含有理想碳-碳键的产品。他还使用这些化合物来系统地研究它们的结构和反应性之间的关系，以便对控制它们行为的原理有一个基本的理解。这些进步帮助美国保持在能源经济的前沿。Agapie小组参与了加州帕萨迪纳市高中生的外展活动。他们支持加州理工学院的课堂联系，与马歇尔基础高中的教师发展关系。高中生的参观和关于科学职业的研讨会吸引了学生从事STEM职业。本科生参加加州理工学院安进和WAVE计划下的项目，该项目的目标是提供研究机会，促进在科学领域代表性不足的学生在科学领域的职业生涯。除了技术培训，研究生还通过与本科生合作来发展他们的指导技能，为培养有才华的劳动力做出贡献。阿加皮博士正在系统地研究一系列钼配合物的结构-反应关系，以期对控制CO和CO2还原偶联和脱氧的选择性的设计原则有一个基本的理解。显示存储电子和改变配位模式的能力的配体结构正在准备中。对机械论和配体设计假设进行了验证，以确定给体的性质、配体的不稳定性、还原电位和亲电性对CO裂解和偶联反应结果的影响。目标是使用实际应用所必需的温和试剂。正在处理的具体挑战包括：1)确定配体对CO裂解的影响，以生成金属碳化物；2)确定控制CO同源作用程度的结构特征(C2与C3等)；3)确定使用温和条件(H+、H-、H2)从观察到的中间体生成CN(n大于或等于2)产物的途径；4)评估与实际应用有关的试剂，如作为亲电荷质子以及氢化物和H2作为质子和电子源的试剂。这些研究可能为设计廉价和实用的催化剂提供必要的基础知识，以将碳原料升级为更高价值的化学品和燃料。这个项目是由本科生和研究生进行的，让他们接触到几个技术领域，包括合成、光谱学和机械研究，所有这些都促进了训练有素的劳动力的发展。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Carbon Dioxide Reduction with Dihydrogen and Silanes at Low-Valent Molybdenum Terphenyl Diphosphine Complexes: Reductant Identity Dictates Mechanism

• DOI: 10.1021/acscatal.1c02922
• 发表时间: 2021-10
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Joshua A. Buss;Naoki Shida;Tianyi He;T. Agapie

Terminal, Open-Shell Mo Carbide and Carbyne Complexes: Spin Delocalization and Ligand Noninnocence

• DOI: 10.1021/jacs.1c03806
• 发表时间: 2021-08-11
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Bailey, Gwendolyn A.;Buss, Joshua A.;Agapie, Theodor
• 通讯作者: Agapie, Theodor

A hemilabile diphosphine pyridine pincer ligand: σ- and π-binding in molybdenum coordination complexes

半稳定二膦吡啶钳配体：钼配位配合物中的α-和α-结合

• DOI: 10.1016/j.poly.2020.114631
• 发表时间: 2020
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Wan, Ruomeng;Buss, Joshua A.;Horak, Kyle T.;Agapie, Theodor
• 通讯作者: Agapie, Theodor

CO Coupling Chemistry of a Terminal Mo Carbide: Sequential Addition of Proton, Hydride, and CO Releases Ethenone

• DOI: 10.1021/jacs.9b07743
• 发表时间: 2019-10-02
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Buss, Joshua A.;Bailey, Gwendolyn A.;Agapie, Theodor
• 通讯作者: Agapie, Theodor

Heterometallic uranium/molybdenum nitride synthesis via partial N-atom transfer

• DOI: 10.1039/d2cc00473a
• 发表时间: 2022-03-10
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Barluzzi, Luciano;Jori, Nadir;Mazzanti, Marinella
• 通讯作者: Mazzanti, Marinella