Bond Making and Bond Breaking Processes at Transition Metal Centers

通过这个奖项，无机、生物无机和有机金属化学项目支持蒙大拿大学化学系爱德华·罗森伯格博士对过渡金属喹啉配合物的研究。首先，研究过渡金属活化的喹啉类化合物亲核加成过程中碳-碳键形成的合成和机理。一些三锇喹啉配合物在喹啉环的5位发生亲核加成区域选择性和立体选择性。这一反应将在有机合成中得到潜在的应用。喹啉衍生物与多金属位络合的碳氮键裂解也将被研究。连续氢化反应的产物将被测定。在第三个项目中，动力学同位素方法将用于确定在化学计量学和催化过程中控制氢向金属转移和从金属转移的因素。质子势垒隧道将被认为是一种可能的途径。本项目涉及催化、天然产物合成、燃料升级等领域。与喹啉形成碳键的新方法可用于合成神经递质激动剂或细胞毒性化合物。研究碳氮键在加氢过程中的行为，可以为加氢脱氮催化反应提供新的认识，这对石油工业具有重要意义。

With this award, the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on transition metal quinoline complexes by Dr. Edward Rosenberg of the Chemistry Department, University of Montana. First, the synthesis and mechanism of carbon-carbon bond-forming during nucleophilic addition to transition metal-activated quinolines will be investigated. Some triosmium quinoline complexes undergo nucleophilic addition regio- and stereoselectively at the 5-position of the quinoline ring. This reaction will be exploited for potential applications in organic synthesis. Carbon-nitrogen bond cleavage in quinoline derivatives complexed to polymetallic sites will also be studied. The products of successive hydrogenations will be determined. In a third project, kinetic isotope methods will be used to determine factors controlling hydrogen transfer to and from metals in stoichiometric and catalytic processes. Proton barrier tunneling will be considered as a possible pathway. This project is relevant to catalysis, natural product synthesis, and fuels upgrading. New methods for forming carbon bonds to quinoline could be applicable to the synthesis of neurotransmitter agonists or cytotoxic compounds. Investigation of the behavior of carbon-nitrogen bonds during hydrogenation may provide insight into the hydrodenitrogenation catalysis reaction, which is important to the petroleum industry.