SusChEM: Utilizing Iron-Coenzyme Oxygen Activation in Catalysis

波士顿大学的John P. Caradonna教授在化学系化学催化（CAT）项目的支持下，研究在可持续的金属基系统中直接利用双氧的新氧化过程，以防止非选择性自由基链反应。本研究开发并表征了一个单核铁配合物家族，该家族利用双氧（4-5次周转）生产铁基反应物质，能够在牺牲双电子给体（如-酮酸）存在的情况下氧化碳氢键。研究集中在烷烃氧化的两个基本不同但相关的方面：1)发展对这些单核非血红素铁络合物激活双氧形成金属基氧化剂的机制的分子水平理解，2)创建第二代络合物，将支持这些系统的形式氧原子转移反应性的一般合成使用。在这些催化系统中使用铁尤其具有吸引力，因为这种金属在地球上储量丰富且无毒，因此，这一努力为工业感兴趣的廉价和可持续的催化转化开辟了新的途径。总的来说，这些努力使人们对基本的反应化学有了更深入的了解，并导致了对诸如烷烃和芳烃等底物的可控氧化有用试剂的开发。Caradonna教授和他的研究小组积极参与美国国家科学基金会资助的PROSTARS项目，该项目由社区大学生在生物/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科学与工程高中研究实习计划。最后，研究者指导和鼓励最近的博士毕业生，他们的研究生生涯显示出他们在化学教学和研究方面的未来卓越潜力，通过波士顿大学博士后教师研究员（PFF）计划。这些研究活动和教育项目共同为培养对可持续化学感兴趣的下一代科学家提供了广泛的经验、深入的知识、环境和工业见解以及必要的沟通技巧。

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.