1,2-Addition of C-H Bonds Across Metal-Heteroatom Bonds: Study of Reactions Central to Hetero-Functionalization of C-H Bonds

无机化学、生物无机化学和金属有机化学项目的这一研究奖支持了弗吉尼亚大学的T.Brent Gunnoe教授探索过渡金属络合物激活碳氢键的工作。形式上，与高d电子数过渡金属配位的阴离子杂原子配体表现出与高度碱性和亲核性特征一致的反应模式。这一特点可能被用来开发新的C-H活化和官能化催化剂，而C-H键在金属-杂原子键上的1，2-加成反应的机理研究将为开发碳氢功能化催化剂提供关键的基础细节。我们的策略是建立多个基于过渡金属的平台，在这些平台上研究C-H活化转化，以努力了解金属同一性、氧化态和杂原子配体同一性对反应速度和底物选择性的影响。该研究计划将为本科生和研究生提供在有机金属化学和均相催化剂开发领域的培训基础。此外，拟议研究的一部分是与主要是本科院校的PI合作进行的，从而为本科生提供了获得生产性研究经验的机会。碳氢化合物的选择性官能化对商品化工部门、精细化学合成和作为能源的化石燃料的有效利用非常重要。碳氢化合物选择性杂官能化的新方法可以提供具有广泛影响的重要的新的合成范例。

This Research award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor T. Brent Gunnoe at the University of Virginia to probe the activation of carbon-hydrogen bonds by transition metal complexes. Formally anionic heteroatomic ligands coordinated to high d-electron count transition metals exhibit reactivity patterns consistent with highly basic and nucleophilic character. This feature can potentially be exploited to develop new catalysts for C-H activation and functionalization, and the mechanistic studies of the 1,2-addition of C-H bonds across metal-heteroatom bonds will provide fundamental details that are key to the development of catalysts for hydrocarbon functionalization. The strategy is to build multiple transition metal based platforms upon which to study the C-H activation transformations in an effort to develop an understanding of the impact of metal identity, oxidation state and heteroatom ligand identity on the reaction rates and substrate selectivity. The research program will provide a training ground for undergraduate and graduate students in the areas of organometallic chemistry and development of homogeneous catalysts. In addition, a portion of the proposed research is in collaboration with a PI from a primarily undergraduate institution, thereby providing undergraduates with an opportunity for a productive research experience.The selective functionalization of hydrocarbons is important to the commodity chemical sector, fine chemical synthesis and the efficient utilization of fossil fuels as energy resources. New methods for selective hetero-functionalization of hydrocarbons can provide important new synthetic paradigms with broad impact.