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

这个研究奖在无机，生物无机和有机化学计划支持教授T。弗吉尼亚大学的布伦特冈诺研究了过渡金属络合物对碳氢键的活化作用。 与高d-电子数过渡金属配位的形式阴离子杂原子配体表现出与高度碱性和亲核特性一致的反应模式。 这一特性可用于开发新型C-H活化和功能化催化剂，C-H键在金属-杂原子键间的1，2-加成机理研究将为开发烃功能化催化剂提供关键的基础细节。 该策略是建立多个过渡金属为基础的平台上，研究C-H活化转化，努力发展的金属身份，氧化态和杂原子配体身份的反应速率和底物选择性的影响的理解。 该研究计划将为有机金属化学和均相催化剂开发领域的本科生和研究生提供培训基地。 此外，一部分拟议的研究是在合作与PI从一个主要的本科院校，从而为本科生提供了一个机会，一个富有成效的研究experience.The选择性功能化的碳氢化合物是重要的商品化学品部门，精细化学品合成和有效利用化石燃料作为能源资源。 用于烃的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.