CAREER: Computational and Experimental Mechanistic Approach to Iron Catalyst and Reaction Design

职业：铁催化剂和反应设计的计算和实验机理方法

• 批准号: 2221728
• 负责人: Osvaldo Gutierrez
• 金额: $ 65万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-03-15 至 2023-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2221728&HistoricalAwards=false
• 关键词: CAREER; Computational; Experimental; Mechanistic; Approach

In this CAREER project, funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Osvaldo Gutierrez of the Department of Chemistry at the University of Maryland College Park is using computational and experimental tools to elucidate the mechanisms of iron-catalyzed carbon bond forming reactions. Carbon bond forming reactions are important in pharmaceutical and other fine chemical products; However, such reactions often require the use of rare and expensive metals. Replacement of the expensive metals in these processes with earth-abundant and non-toxic iron is the goal of this project. In addition to the research activities, Professor Gutierrez is piloting a partnership between the University and the nearby Prince George's Community College to encourage community college students to conduct hands-on summer research at University of Maryland and to train community college faculty to use and implement modern computational tools in undergraduate education. These efforts are further enhanced with the Alliance for Diversity in Science and Engineering. Knowledge of the mechanisms of iron-catalyzed processes is rudimentary, thus hindering rational catalyst design. This hypothesis-driven project focuses on performing mechanistic studies designed to increase understanding of the factors that control reactivity and selectivity. in carbon-bond forming reactions. By performing both calculations and synthesis in one laboratory setting, Professor Osvaldo Gutierrez and his research team are well positioned to address new developments from both the computational or experimental sides of the research to gain a far-reaching picture of the factors controlling product selectivity. Specific research goals include the use quantum mechanical calculations and chemical synthesis of mechanistic probes to elucidate the mechanisms of iron-catalyzed carbon-carbon cross-coupling reactions. The team also seeks to develop predictive models, based on transition state calculations, of reactivity and selectivity of iron-catalyzed carbon-carbon double bond functionalization. The researchers also establish guiding principles for predicting geometry and spin states of diamine bispyridine iron(II) catalysts. This project may lead to foundational catalyst design principles for broader applications in catalytic chemical synthesis.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.

在这个由化学部化学结构、动力学和机制 B 项目资助的职业项目中，马里兰大学帕克分校化学系的 Osvaldo Gutierrez 教授正在使用计算和实验工具来阐明铁催化的机制碳键形成反应。 碳键形成反应在医药和其他精细化工产品中很重要；然而，此类反应通常需要使用稀有且昂贵的金属。 该项目的目标是用地球上储量丰富且无毒的铁替代这些过程中的昂贵金属。 除了研究活动外，古铁雷斯教授还在该大学与附近的乔治王子社区学院之间试行合作，鼓励社区学院的学生在马里兰大学进行实践暑期研究，并培训社区学院教师使用和实施现代技术本科教育中的计算工具。科学与工程多样性联盟进一步加强了这些努力。 对铁催化过程机理的了解还很初级，因此阻碍了合理的催化剂设计。这个假设驱动的项目侧重于进行机制研究，旨在增进对控制反应性和选择性的因素的理解。在碳键形成反应中。通过在一个实验室环境中进行计算和合成，Osvaldo Gutierrez 教授和他的研究团队能够很好地解决研究的计算或实验方面的新发展，以获得控制产品选择性的因素的深远图景。具体研究目标包括利用量子力学计算和机械探针的化学合成来阐明铁催化碳-碳交叉偶联反应的机制。 该团队还寻求基于过渡态计算开发铁催化碳-碳双键官能化的反应性和选择性的预测模型。 研究人员还建立了预测二胺双吡啶铁（II）催化剂的几何形状和自旋态的指导原则。该项目可能会产生在催化化学合成中更广泛应用的基本催化剂设计原则。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。