164112-72-5Relevant articles and documents
Heterolytic Oxidative Addition of sp2and sp3C-H Bonds by Metal-Ligand Cooperation with an Electron-Deficient Cyclopentadienone Iridium Complex
Higashi, Takuya,Kusumoto, Shuhei,Nozaki, Kyoko
supporting information, p. 12999 - 13004 (2021/08/16)
Oxidative addition reactions of C-H bonds that generate metal-carbon-bond-containing reactive intermediates have played essential roles in the field of organometallic chemistry. Herein, we prepared a cyclopentadienone iridium(I) complex 1 designed for oxidative C-H bond additions. The complex cleaves the various sp2 and sp3 C-H bonds including those in hexane and methane as inferred from their H/D exchange reactions. The hydroxycyclopentadienyl(nitromethyl)iridium(III) complex 2 was formed when the complex was treated with nitromethane, which highlights this elementary metal-ligand cooperative C-H bond oxidative addition reaction. Mechanistic investigations suggested the C-H bond cleavage is mediated by polar functional groups in substrates or another iridium complex. We found that ligands that are more electron-deficient lead to more favorable reactions, in sharp contrast to classical metal-centered oxidative additions. This trend is in good agreement with the proposed mechanism, in which C-H bond cleavage is accompanied by two-electron transfer from the metal center to the cyclopentadienone ligand. The complex was further applied to catalytic transfer-dehydrogenation of tetrahydrofuran (THF).
Silver-Catalyzed C-H Trifluoromethylation of Arenes Using Trifluoroacetic Acid as the Trifluoromethylating Reagent
Shi, Guangfa,Shao, Changdong,Pan, Shulei,Yu, Jingxun,Zhang, Yanghui
supporting information, p. 38 - 41 (2015/07/28)
Direct trifluoromethylation of arenes using TFA as the trifluoromethylating reagent was achieved with Ag as the catalyst. This reaction not only provides a new protocol for aryl C-H trifluoromethylation, but the generation of CF3· from TFA may prove useful in other contexts and could potentially be extended to other trifluoromethylation reactions. (Chemical Equation Presented).
