CAREER: Iron- and Cobalt-Catalyzed Direct C-H Functionalization

罗彻斯特大学（University of Rochester）的Michael Neidig教授在化学催化项目资助下，对铁和钴催化的碳氢直接官能化的活性物质和催化机制进行了详细的分子水平研究。虽然基于廉价、富含地球的金属的催化剂为这些转化提供了巨大的潜力，但对铁和钴催化的直接碳氢官能化的结构、键和机制的基本见解的发展对于启发和促进合理设计和开发具有改进催化性能的系统至关重要。该项目结合了多种无机光谱（磁圆二色、穆斯堡尔、电子顺磁共振、共振拉曼）、密度泛函理论、合成、动力学和反应研究，详细阐明了活性催化剂种类和铁和钴催化剂直接碳氢功能化的机制。被研究的反应包括C(sp2)-H和C(sp3)-H烷基化和芳化以及C(sp2)-H胺化。这项工作的更广泛的影响包括对活性催化剂形态和机制的潜在基本见解，以启发和促进基于毒性更小、富含地球的金属的改进催化剂系统的发展，用于替代能源、制药和材料科学。本研究为学生提供了物理无机化学和催化方面的训练基础。此外，Neidig教授开发的外展项目为来自罗切斯特市学区的代表性不足的高中生以及门罗社区学院的本科生和教师提供了研究机会。

AbstractIn this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Michael Neidig of the University of Rochester is developing detailed molecular level insight into the active species and mechanisms of catalysis in iron- and cobalt-catalyzed direct C-H functionalizations. While catalysts based on inexpensive, earth abundant metals offer tremendous potential for these transformations, the development of fundamental insight into structure, bonding and mechanism in iron- and cobalt-catalyzed direct C-H functionalization is critical to inspire and facilitate the rational design and development of systems with improved catalytic performance. The project combines multiple inorganic spectroscopies (magnetic circular dichroism, Mossbauer, electron paramagnetic resonance, resonance Raman), density functional theory, synthesis and kinetic and reaction studies to elucidate detailed insight into the active catalyst species and the mechanisms involved in direct C-H functionalization by iron and cobalt catalysts. Reactions being investigated include C(sp2)-H and C(sp3)-H alkylations and arylations as well as C(sp2)-H aminations.The broader impacts of this work include the potential for fundamental insight into active catalyst speciation and mechanism to inspire and facilitate the development of improved catalyst systems based on less toxic, earth abundant metals for applications in alternative energy, pharmaceuticals and materials science. The research provides a training ground for students in physical-inorganic chemistry and catalysis. In addition, an outreach program developed by Professor Neidig provides research opportunities for underrepresented high school students from the Rochester City School District as well as Monroe Community College undergraduates and faculty.