Nonclassical Oxygenation Reactions

非经典氧化反应

• 批准号: 1112356
• 负责人: Seth Brown
• 金额: $ 41.1万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-09-01 至 2015-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1112356&HistoricalAwards=false
• 关键词: Nonclassical; Oxygenation; Reactions

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.

化学部的这一奖项支持了Seth N.布朗在圣母大学探索非经典的氧化反应激活的单核细胞中心。主要策略是基于使用氧化还原活性配体，这些配体使用小的咬合角来鼓励钼和钨复合物上更高的配位数。 配体将包括已知的（儿茶酚盐、双（亚氨基苯氧化物）、酰胺基双（苯氧化物））和新的（六齿三-（亚氨基苯氧化物）、双（羟基苯基）三唑）设计。分子氧与还原配体的配合物的相互作用，以及可能的分子氧生成从氧化配体的二氧代配合物，将进行机械研究。还将分析配体-氧化的氧代络合物将氧递送至底物的能力，以确定促进该反应的几何和电子因素。结合联合收割机分子氧活化与原子转移到有机底物的可能的催化反应，如烯烃的氧化裂解（即，使用分子氧的臭氧分解）。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中具有影响。这是一个困难的目标，因为分子氧的中间氧化态（如过氧化物）能量高，对有效反应设置了内在障碍。 这项研究将为博士后、研究生和本科生提供广泛的培训。 本科生（包括代表性不足的群体的成员）将被招募，并鼓励他们在整个本科生涯中从事研究。 研究生，特别是博士后学者将被鼓励与PI合作指导本科生，以协助他们的培训，并为他们提供追求教学和研究事业的动力。

项目成果

Nonclassical oxygen atom transfer reactions of an eight-coordinate dioxomolybdenum( vi ) complex

八配位二氧钼( vi )配合物的非经典氧原子转移反应

• DOI: 10.1039/d1qi00308a
• 发表时间: 2021
• 期刊: Inorganic Chemistry Frontiers
• 影响因子: 7
• 作者: Ranis, Leila G.;Gianino, Jacqueline;Hoffman, Justin M.;Brown, Seth N.
• 通讯作者: Brown, Seth N.

On the border between localization and delocalization: tris(iminoxolene)titanium( iv )

定位与离域的边界：tris(iminoxolene)titanium( iv )

• DOI: 10.1039/c8dt04528c
• 发表时间: 2019
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Marshall-Roth, Travis;Yao, Kun;Parkhill, John A.;Brown, Seth N.
• 通讯作者: Brown, Seth N.