Catalytic Activation of C-H/C-C Bonds by Electrophilic Metal Compounds

宾夕法尼亚州立大学的Ayusman Sen获得了无机、生物无机和有机金属化学项目的奖项，以表彰他对碳氢化合物中导致烷烃和芳烃氧化官能化的碳氢键和碳碳键的金属介导亲电活化的研究。尤其重要的是，这项研究的潜在成果将是甲烷催化氧化制甲醇，这是一种优良且方便运输的能源。一般的方法是在三氟乙酸溶剂中采用高亲电性、弱连接的金属物质，如镧系（III）三氟乙酸配合物。这项研究将涉及五个主要问题：(a)引起c - h键亲电分裂的倾向与金属性质之间的关系，(b)不同类别的c - h键进行亲电分裂的相对倾向，(c)不同类型的助氧化剂在催化循环中再氧化金属的能力，(d)将金属单独用作亲电试剂和单独的双电子氧化剂来氧化金属结合的烃基的可能性，以及(e)实现C-C键的亲电裂解的可能性。

This award to Ayusman Sen of The Pennsylvania State University from the Inorganic, Bioinorganic and Organometallic Chemistry Program is for study of metal mediated electrophilic activation of carbon-hydrogen and carbon-carbon bonds in hydrocarbons leading to the oxidative functionalization of alkanes and arenes. Especially important as a potential outcome of this research would be the catalytic oxidation of methane to methanol, an excellent and conveniently transportable energy source. The general approach will be to employ highly electrophilic, weakly ligated metal species such as the lanthanide(III) tri- fluoroacetate complexes in trifluoroacetic acid solvent. The study will address five major points: (a) the relationship between the propensity to cause electrophilic cleavage of C-H bonds and the nature of the metal, (b) the relative tendencies of the different classes of C-H bonds to undergo electrophilic cleavage, (c) the ability of different types of cooxidants to reoxidize the metal species in the catalytic cycle, (d) the possibility of using the metal solely as an electrophile and a separate two-electron oxidant to oxidize the metal-bound hydrocarbyl species, and (e) the possibility of achieving the electroplilic cleavage of C-C bonds.