New Reaction Chemistry with Transition Metal Complexes for Conversion of Oxygenated

加州理工学院的Theodor Agapie博士在化学系化学合成项目的资助下，正在合成分子化合物，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）是特别理想的，因为它们使美国经济能够维持其现有的能源基础设施。虽然用于将CO转化为含有碳-碳键的燃料的催化剂是已知的，但它们的反应在化学上具有挑战性并且知之甚少。Agapie博士的催化剂能够使用CO作为起始材料形成含有所需碳-碳键的产物。他还使用这些化合物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了解。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高中学生的外展活动。 他们支持加州理工学院的课堂连接，发展与教师的关系，作为马歇尔基础高中。 高中生的访问和关于科学职业的研讨会使学生参与STEM职业。 本科生参加加州理工学院安进和WAVE计划下的项目，这些项目的目标是提供研究机会，以促进在科学领域代表性不足的学生从事科学职业。 除了技术培训，研究生通过与本科生合作来培养他们的指导技能，为人才队伍的教育做出贡献。Agapie博士正在系统地研究钼络合物家族的结构-反应性关系，以便对控制CO和CO2还原偶联和脱氧选择性的设计原理有一个基本的了解。显示存储电子和改变配位模式的能力的配体结构正在制备中。机制和配体设计假设进行测试，以确定捐助者的性质，配体不稳定性，还原电位，和亲电试剂的CO裂解和偶联反应的结果的影响。有针对性地使用实际应用所必需的温和试剂。目前正在解决的具体挑战包括：1）确定配体对CO裂解产生金属碳化物的影响; 2）确定控制CO同系化程度的结构特征（C2 vs C3等）; 3）确定Cn的途径（n大于或等于2）使用温和条件从观察到的中间体生成产物（H+，H-，H2）; 4）评估与实际应用相关的试剂，例如作为亲电体的质子，以及作为质子和电子源的氢化物和H2。这些研究可以为设计廉价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。该项目由本科生和研究生进行，使他们接触到几个技术领域，包括合成、光谱和机械研究，所有这些都有助于培养训练有素的劳动力。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。

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.