Nonclassical Oxygenation Reactions

该奖项支持圣母大学塞思·N·布朗教授探索非经典氧化反应激活单金属中心的研究。主要的策略是使用氧化还原活性配体，这些配体使用小咬合角来鼓励钼和钨的络合物上更高的配位数。配体将包括已知的(儿茶酚、双(亚氨基苯氧基)、酰胺双(苯氧基))和新的(十六齿三-(亚氨基苯氧基)、双(羟基苯基)三唑)构型。分子氧与还原配体的络合物的相互作用，以及氧化配体的二氧基络合物可能产生的分子氧，将从力学上进行研究。还将分析配体氧化的氧络合物向底物输送氧气的能力，以确定鼓励这一反应的几何和电子因素。将探索将分子氧活化与原子转移到有机底物相结合的可能的催化反应，例如烯烃的氧化裂解(即使用分子氧进行臭氧分解)。这项研究探索了更有效地合成含氧有机分子的方法。活化分子氧是催化的主要目标，在绿色化学合成和可再生能源储存方面具有影响。这是一个困难的目标，因为二氧化碳的中间氧化态(如过氧化氢)能量很高，这在本质上阻碍了有效的反应。该研究将为博士后、研究生和本科生提供广泛的培训。本科生(包括代表性不足群体的成员)将被招募，并鼓励他们在本科职业生涯中从事研究。将鼓励研究生，特别是博士后学者与PI合作指导本科生，以帮助他们进行培训，并为他们提供从事教学和研究事业的动力。

This award in the Division of Chemistry supports research by Professor Seth N. Brown at the University of Notre Dame to explore the activation of monometallic centers by nonclassical oxygenation reactions. The main strategy is based on using redox-active ligands that use small bite angles to encourage higher coordination numbers on complexes of molybdenum and tungsten. Ligands will include both known (catecholate, bis(iminophenoxide), amidobis(phenoxide)) and novel (hexadentate tris- (iminophenoxide), bis(hydroxyphenyl)triazole) designs. Interactions of molecular oxygen with complexes of the reduced ligands, as well as possible molecular oxygen generation from dioxo complexes of the oxidized ligands, will be studied mechanistically. The ability of the ligand-oxidized oxo complexes to deliver oxygen to substrates will also be analyzed to determine the geometric and electronic factors that encourage this reaction. Possible catalytic reactions that combine molecular oxygen activation with atom transfer to organic substrates, such as oxidative cleavage of alkenes (i.e., ozonolysis using molecular oxygen), will be explored. This research explores ways to synthesize oxygen-containing organic molecules more efficiently. Activating molecular oxygen is a prime target for catalysis, with impacts in green chemical synthesis and renewable energy storage. It is a difficult target because the intermediate oxidation states of dioxygen (such as peroxide) are high in energy, placing an intrinsic roadblock on efficient reactions. The research will provide broad training of postdoctoral, graduate, and undergraduate students. Undergraduates (including members of underrepresented groups) will be recruited and encouraged to pursue research throughout their undergraduate careers. Graduate students and especially postdoctoral scholars will be encouraged to mentor undergraduates in collaboration with the PI in order to assist in their training and provide them with motivation to pursue careers in teaching and research.