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.

该奖项在化学系中支持巴黎圣母院的塞思·布朗教授的研究，以探索非经典氧合反应的一元中心的激活。主要策略是基于使用氧化还原活性的配体，这些配体使用小咬合角来鼓励对钼和钨络合物的更高配位数。 配体将包括已知的（儿茶素，双苯二酚），胺（苯氧化物））和新颖（己二酸六氧化物），BIS（羟基苯基）设计。分子氧与还原配体的络合物以及从氧化配体的二氧配合物中产生的分子氧的相互作用将被机械地研究。还将分析富含配体氧化的Oxo复合物向底物输送氧气的能力，以确定鼓励这种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的可能的催化反应，例如探索烷烃的氧化性裂解（即使用分子氧的臭氧溶解）。这项研究探讨了更有效地合成含氧的有机分子的方法。激活分子氧是催化的主要靶标，对绿色化学合成和可再生能量储存产生了影响。这是一个困难的目标，因为二氧化物的中间氧化态（例如过氧化物）的能量很高，在有效反应上置于内在的障碍。 这项研究将为博士后，研究生和本科生提供广泛的培训。 将招募并鼓励本科生（包括代表性不足的群体的成员）在整个本科职业中从事研究。 鼓励研究生，尤其是博士后学者与PI合作指导本科生，以协助他们的培训，并为他们提供从事教学和研究职业的动力。

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.