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教授得到了化学催化（CAT）化学划分的支持，以研究直接在可持续金属系统中直接利用二氧化物的新氧化过程，这些系统排除了非选择性的自由基链反应。这项研究开发并表征了一个单核铁络合物家族，该家族利用二氧化物（4-5个失误）来生产基于铁的反应性物种，该物种能够在存在牺牲的两电子供体配体（例如-keto acid）的情况下能够氧化碳氧化碳（C-H）键。 该研究的重点是烷烃氧化的两个基本不同的两种不同的方面：1）对这些单核非血浆铁络合物通过这种机制的理解的发展，使这些机制激活了二氧化基因，形成了基于金属的氧化剂，以及2）2）将建立二级式氧化系统的形式构成形式的氧化基因的反应。在这些催化系统中使用铁特别有吸引力，因为这种金属具有土壤丰富的和无毒的性，因此，这种努力在廉价且可持续的催化转型中开辟了新的途径。总体而言，这项工作使人们对基本反应化学的理解有了更深入的了解，并导致开发有用的试剂，以控制碱和领域等底物的氧化。 Caradonna教授及其研究小组积极参加了NSF资助的妓女计划，在该计划中，社区大学生在生物/化学方面的实验室中进行研究。 他的实验室还为学生提供了最早的研究机会，并每年参加波士顿大学的科学与工程学高中研究实习计划。 最后，调查员指导并鼓励最近的博士学位。毕业生的研究生职业表现出了他们在波士顿大学的博士后教师（PFF）计划中表现出在化学教学和研究中的未来卓越潜力。研究活动和教育项目共同产生了广泛的经验，知识，环境和工业见解的深度以及对发展具有可持续化学兴趣的下一代科学家所必需的沟通技巧。