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

在化学系化学催化计划资助的这一项目中，罗切斯特大学的Michael Neidig教授正在对铁和钴催化的直接C-H官能化反应中的活性物种和催化机理进行详细的分子水平的研究。虽然基于廉价、地球丰富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C-H官能化的结构、键合和机制的基本见解的发展对于激发和促进具有改进的催化性能的系统的合理设计和开发至关重要。该项目结合了多种无机光谱（磁性圆二色性，穆斯堡尔，电子顺磁共振，共振拉曼），密度泛函理论，合成和动力学和反应研究，以阐明详细的洞察力的活性催化剂物种和机制参与直接C-H功能化的铁和钴催化剂。正在研究的反应包括C（sp2）-H和C（sp3）-H烷基化和芳基化以及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理的基本洞察的潜力，以启发和促进基于低毒性、地球丰富的金属的改进催化剂系统的开发，用于替代能源、制药和材料科学。本研究为物理-无机化学和催化专业的学生提供了一个训练基地。此外，由Neidig教授开发的外展计划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.