Non-Heme Iron Oxygen Atom Transfer Catalysis

该奖项在无机，生物无机和有机化学计划支持工作由约翰P Caradonna探索一类双核非血红素亚铁配合物所表现出的化学，这些配合物能够在氧原子供体分子或烷基氢过氧化物的存在下催化烷烃氧化为醇。 催化烷烃氧化和官能化是一个具有强烈科学和商业兴趣的领域，这是由于将廉价的脂族烃转化为有价值的化学和燃料产品的潜力。 所提出的方法使用合成，机械和光谱方法的组合来研究复合物的催化化学，这些复合物是基于从金属酶研究中获得的原理设计的，并且模拟了许多非血红素铁单加氧酶所表现出的两个基本过程。 这些过程是结合的过氧化物配体的异裂断裂和氧原子向底物的有效转移。 这项工作的重点是两个根本不同的，但相关的烷烃氧化方面：1）发展对双核亚铁化合物催化烷烃和芳烃氧化的机制的分子水平理解，和2）探索铁基反应性中间体的化学性质和电子特性尽管烷烃和生物材料是有吸引力的原料，但由于用于它们改性的可用反应数量有限，它们的用途目前主要限于燃料。 这项工作是针对一个更深入的了解基本的反应化学和有用的试剂，如烷烃和芳烃的底物的控制氧化的发展。 该项目还为研究生和本科生提供了一个参与协作学习环境的机会。 作为美国化学学会种子计划的参与者，Caradonna教授还向少数民族高中生开放了他的实验室，他们进行了为期10周的研究，在研究中，他们也接触到了一般的大学生活。 与拟议的计划和Caradonna教授的教育项目相关的研究活动产生了广泛的经验，知识的深度和有成就的年轻科学家的发展所需的沟通技巧。

This award in Inorganic, Bioinorganic and Organometallic Chemistry program supports work by John P. Caradonna to explore the chemistry exhibited by a class of binuclear non-heme ferrous complexes that are capable of catalyzing the oxidation of alkanes to alcohols in the presence of either oxygen atom donor molecules or alkyl hydroperoxides. Catalytic alkane oxidation and functionalization is an area of intense scientific and commercial interest due the potential for converting inexpensive aliphatic hydrocarbons to valuable chemical and fuel products. The proposed approach uses a combination of synthetic, mechanistic, and spectroscopic methods to investigate the catalytic chemistry of complexes, which are designed based on principles obtained from metalloenzyme studies and mimic two fundamental process exhibited by many non-heme iron monooxygenases. These processes are the heterolytic cleavage of a bound peroxide ligand and the efficient transfer of the oxygen atom to substrate. The work focuses on two fundamentally different, although related aspects of alkane oxidation: 1) Development of a molecular-level understanding of the mechanism by which binuclear ferrous compounds catalyze the oxidation of alkanes and arenes, and 2) Exploration of the chemical nature and electronic characteristics of the iron-based reactive intermediate(s) responsible for the formal transfer of an oxygen atom to an alkane substrate.Although alkanes and biological materials are attractive feedstocks, their use is currently restricted primarily to fuels because of the limited number of available reactions for their modification. This work is directed toward a deeper understanding of the fundamental reaction chemistry and the development of useful reagents for the controlled oxidation of substrates such as alkanes and arenes. This project also affords an opportunity for graduate and undergraduate students to participate in a collaborative learning environment. As a participant in the American Chemical Society's SEED program, Prof. Caradonna has also opened his laboratory to minority high school students who perform 10 weeks of research in which they are also exposed to college life in general. The research activities associated with the proposed program and Professor Caradonna's educational projects generate a wide range of experiences, depth of knowledge, and communication skills necessary for the development of accomplished young scientists.