SusChEM: Utilizing Iron-Coenzyme Oxygen Activation in Catalysis

SusChEM：在催化中利用铁辅酶氧活化

• 批准号: 1300122
• 负责人: John Caradonna
• 金额: $ 42万
• 依托单位: Trustees of Boston University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-07-01 至 2017-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1300122&HistoricalAwards=false
• 关键词: SusChEM; Utilizing; Iron; Coenzyme; Oxygen

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.

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式反应。这项研究开发并表征了一系列单核铁配合物，这些配合物利用双氧（4-5 周转）来生产铁基活性物质，该活性物质能够在牺牲双电子存在的情况下氧化碳-氢 (C-H) 键。供体配体，例如-酮酸。 该研究重点关注烷烃氧化的两个基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氧化剂的机制进行分子水平的理解，以及2）第二代复合物的创建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。在这些催化系统中使用铁特别有吸引力，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且可持续的催化转化开辟了新途径。总体而言，这些努力使人们对基本反应化学有了更深入的了解，并导致开发出用于控制烷烃和芳烃等底物氧化的有用试剂。 Caradonna 教授和他的研究小组积极参与 NSF 资助的 PROSTARS 计划，在该计划中，社区学院的学生在生物/化学导向的实验室中进行研究。 他的实验室还尽早为学生提供研究机会，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，研究者指导和鼓励最近的博士学位。通过波士顿大学的博士后研究员 (PFF) 计划，毕业生的职业生涯已显示出他们未来在化学教学和研究方面取得卓越成就的潜力。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培养对可持续化学感兴趣的下一代科学家所必需的沟通技能。