Bond Making and Bond Breaking Processes at Transition Metal Centers

通过该奖项，无机化学、生物无机化学和金属有机化学计划支持蒙大拿大学化学系Edward Rosenberg博士对过渡金属喹啉配合物的研究。首先，我们将研究过渡金属活化的喹啉类化合物亲核加成反应中碳-碳键的合成和形成机理。一些三膦喹啉配合物在喹啉环的5位上发生区域和立体选择性的亲核加成反应。该反应在有机合成中具有潜在的应用前景。还将研究与多金属中心络合的喹啉衍生物中的碳-氮键断裂。将对连续加氢的产物进行测定。在第三个项目中，将使用动力学同位素方法来确定在化学计量和催化过程中控制氢向金属转移和从金属转移的因素。质子势垒隧穿将被认为是一种可能的途径。该项目涉及催化、天然产物合成和燃料升级。与喹啉形成碳键的新方法可能适用于神经递质激动剂或细胞毒性化合物的合成。研究碳氮键在加氢过程中的行为有助于深入了解加氢脱氮催化反应，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.