CAREER: Oxidative Reactivity of Pd and Ni Complexes Employing Paramagnetic Oxidation States

在这个由化学合成和催化计划资助的CAREER奖中，圣路易斯华盛顿大学化学系的Liviu Mirica教授将合成新型顺磁性Pd（III）和Ni（III）配合物，并详细研究它们的电子性质和反应性，长期目标是开发涉及这些不太常见的氧化态的催化转化。特别感兴趣的是Pd介导的有氧氧化C-H官能化反应和详细的反应性研究的有机金属Ni（III）配合物相关的交叉偶联反应。这些研究包括合成有机金属和无机化学，催化，电化学和物理无机光谱学的结合，因此将为学生提供跨学科培训和发展广泛科学技能的机会。此外，这些研究将与外展活动充分结合，这些活动将通过在圣路易斯市区公立学校的讲座和演示，使来自代表性不足群体的学生接触化学。钯和镍络合物可作为合成商品化学品、精细化学品和生物活性化合物所必需的广泛化学反应的催化剂。拟议的研究应该会导致与有机合成相关的独特的金属介导的氧化转化，这可能会影响化学家如何将原子放在一起，以更有效和更经济地构建复杂的分子。

In this CAREER award funded by the Chemical Synthesis and Catalysis Programs, Professor Liviu Mirica of the Department of Chemistry at Washington University in St. Louis will synthesize novel paramagnetic Pd(III) and Ni(III) complexes and investigate in detail their electronic properties and reactivity, with the long-term goal of developing catalytic transformations that involve these less common oxidation states. Of particular interest are Pd-mediated aerobic oxidative C-H functionalization reactions and detailed reactivity studies of organometallic Ni(III) complexes relevant to cross coupling reactions. These studies include a combination of synthetic organometallic and inorganic chemistry, catalysis, electrochemistry, and physical inorganic spectroscopy, and thus will provide the students interdisciplinary training and the opportunity to develop a broad range of scientific skills. In addition, these studies will be fully integrated with outreach activities that will expose students from underrepresented groups to chemistry through lectures and demonstrations at public schools from the St. Louis metro area.Palladium and nickel complexes act as catalysts for a wide range of chemical reactions that are essential for the synthesis of commodity chemicals, fine chemicals, and bioactive compounds. The proposed research should lead to unique metal-mediated oxidative transformations relevant to organic synthesis that may impact how chemists put atoms together to build complex molecules more efficiently and economically.