SusChEM: Utilizing Iron-Coenzyme Oxygen Activation in Catalysis

波士顿大学的John P. Caradonna教授得到了化学系化学催化（CAT）项目的支持，以研究在可持续的金属基系统中直接利用分子氧的新氧化过程，从而避免非选择性自由基链式反应。本研究开发和表征了一个家庭的单核铁络合物，利用分子氧（4-5周转）在生产的铁基活性物种，能够氧化碳-氢（C-H）键的牺牲的两个电子供体配体，如酮酸的存在下。 该研究集中在烷烃氧化的两个根本不同但相关的方面：1）对这些单核非血红素亚铁络合物激活分子氧形成金属基氧化剂的机制的分子水平理解的发展，以及2）创建第二代络合物，这将支持这些系统的正式氧原子转移反应性的一般合成用途。在这些催化体系中使用铁是特别有吸引力的，因为这种金属是地球上丰富的和无毒的，因此，这一努力开辟了工业感兴趣的廉价和可持续的催化转化的新途径。总的来说，这一努力导致了对基本反应化学的更深入理解，并导致了用于底物（如烷烃和芳烃）的受控氧化的有用试剂的开发。Caradonna教授和他的研究小组积极参与NSF资助的PROSTARS计划，社区大学的学生在生物/化学实验室进行研究。 他的实验室还为学生提供尽可能早的研究机会，并每年参加波士顿大学的科学与工程高中研究实习计划。 最后，研究人员指导和鼓励最近的博士学位。毕业生的研究生生涯已经显示出他们的潜力，未来卓越的化学教学和研究，虽然波士顿大学的博士后教员研究员（PFF）计划。研究活动和教育项目共同产生了广泛的经验，知识深度，环境和工业见解以及对可持续化学感兴趣的下一代科学家发展所需的沟通技能。

Professor John P. Caradonna of Boston University is supported by the Chemical Catalysis (CAT) Program in the Division of Chemistry to investigate new oxidation processes that directly utilize dioxygen in sustainable metal-based systems that preclude non-selective free-radical chain reactions. This research develops and characterizes a family of mononuclear iron complexes that utilize dioxygen (4-5 turnovers) in the production of an iron-based reactive species that is capable of oxidizing carbon-hydrogen (C-H) bonds in the presence of sacrificial two-electron donor ligands such as -keto acids. The research focuses on two fundamentally different, although related aspects of alkane oxidation: 1) the development of a molecular-level understanding of the mechanism by which these mononuclear non-heme ferrous complexes activate dioxygen to form a metal-based oxidant, and 2) the creation of second-generation complexes that will support the general synthetic use of the formal oxygen-atom transfer reactivity of these systems. The use of iron in these catalytic systems is particularly attractive as this metal is earth-abundant and non-toxic and thus, this effort opens new avenues in inexpensive and sustainable catalytic transformations of interest to industry. Overall, the effort results in a deeper understanding of fundamental reaction chemistry and leads to the development of useful reagents for the controlled oxidation of substrates such as alkanes and arenes. Professor Caradonna and his research group actively participate in the NSF-funded PROSTARS Program in which community college students perform research in biological/chemical oriented laboratories. His laboratory also offers research opportunities to students at the earliest level possible, and annually participates in the Boston University's High School Research Internship Program in Science and Engineering. Finally, the investigator mentors and encourages recent Ph.D. graduates whose graduate careers have shown their potential for future excellence in both chemistry teaching and research though Boston University's Postdoctoral Faculty Fellow (PFF) program. Together, the research activities and educational projects generate a wide range of experiences, depth of knowledge, environmental and industrial insights, and communications skills necessary for the development of next generation scientists with interests in sustainable chemistry.