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

在这个由化学部化学结构，动力学机制B计划资助的CAREER项目中，马里兰州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碳键形成反应的机制。 碳键形成反应在制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和昂贵的金属。 该项目的目标是用地球上丰富的无毒铁来替代这些过程中的昂贵金属。 除了研究活动外，Gutierrez教授还在大学与附近的乔治王子社区学院之间建立伙伴关系，鼓励社区学院的学生在马里兰州大学进行暑期实践研究，并培训社区学院的教师在本科教育中使用和实施现代计算工具。这些努力通过科学和工程多样性联盟得到进一步加强。 铁催化过程的机理知识是基本的，从而阻碍了合理的催化剂设计。这个假设驱动的项目侧重于执行机制研究，旨在增加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影响。具体的研究目标包括使用量子力学计算和化学合成的机械探针，以阐明铁催化的碳-碳交叉偶联反应的机制。 该团队还寻求开发基于过渡态计算的预测模型，用于铁催化碳碳双键官能化的反应性和选择性。 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状态的指导原则。这个项目可能会导致催化剂设计的基本原则，在催化化学合成中更广泛的应用。这个奖项反映了NSF的法定使命，并已被认为是值得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的支持。

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.