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

职业：利用顺磁氧化态的 Pd 和 Ni 配合物的氧化反应性

• 批准号: 1255424
• 负责人: Liviu Mirica
• 金额: $ 55万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1255424&HistoricalAwards=false
• 关键词: CAREER; Oxidative; Reactivity; Pd; Ni

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.

在这项由化学合成和催化项目资助的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，其长期目标是开发涉及这些不太常见氧化态的催化转化。特别感兴趣的是pd介导的有氧氧化C-H功能化反应和与交叉偶联反应相关的有机金属Ni（III）配合物的详细反应性研究。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的培训和发展广泛的科学技能的机会。此外，这些研究将与外展活动充分结合，这些活动将通过圣路易斯都会区的公立学校的讲座和示范，让代表性不足的群体的学生接触化学。钯和镍配合物作为广泛的化学反应的催化剂，对合成商品化学品、精细化学品和生物活性化合物至关重要。拟议的研究将导致与有机合成相关的独特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经济地构建复杂分子。