Activation of Oxygen: Mechanistic Aspects of Electron Transfer and Atom Transfer

这项由无机化学、生物无机化学和金属有机化学项目颁发的奖项支持爱荷华州立大学化学系的詹姆斯·埃斯彭森和安德里亚·巴卡奇的研究。该项目将探索瞬时和亚稳态氧自由基的化学，它们与过渡金属络合物的相互作用，以及它们在有机氧化反应中的作用。更具体地说，邻苯二甲酰亚胺-N-氧基自由基，Pino*，将被视为工业上重要反应的潜在促进剂，如对二甲苯和其他芳香族化合物的氧化。PINO*可能会取代目前使用的腐蚀性促进剂溴化物。对这些复杂的氧化反应进行详细的机理研究，包括氢原子的提取和电子转移，将有助于我们更好地理解这些基本过程，这项工作对商品和精细化工行业具有潜在的意义。这项研究还将包括对一组无机化合物的研究，这些化合物在氧气活化过程中表现出通常只有在复杂的酶系统中才能观察到的化学变化。氧化和自由基化学与氧化应激、衰老、心脏病、癌症和炎症性疾病有关，因此更好地了解这些非常活跃的物种将有助于药物化学和毒理学。受过自由基化学训练的化学家可以为化学工业和医学做出贡献。

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by James Espenson and Andreja Bakac, Department of Chemistry, Iowa State University. The project will explore the chemistry of transient and metastable oxyl radicals, their interactions with transition metal complexes and their role in organic oxidation reactions. More specifically, the phthalimide-N-oxyl radical, PINO*, will be examined as a potential promoter in industially important reactions such as the oxidation of para-xylene and other aromatic compounds. PINO* could potentially replace the corrosive promoter bromide currently in use. Detailed mechanistic studies of these complicated oxidation reactions, including hydrogen atom abstractions and electron transfers, will help us better understand these fundamental processes.This work has potential implications for the commodity and fine chemicals industries. The research will also include studies of a group of inorganic compounds that, in the process of oxygen activation, exhibit chemical transformations typically observed only in complicated enzymatic systems. Oxidation and free radical chemistry are involved in oxidative stress, aging, heart disease, cancer and inflammatory illnesses, so a better understanding of these very reactive species will benefit medicinal chemistry and toxicology. Chemists trained in free radical chemistry can contribute to both the chemical industry and medicine.