Heterolytic Oxidative Addition of sp and sp C-H Bonds by Metal-Ligand Cooperation with an Electron-Deficient Cyclopentadienone Iridium Complex.

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 designed for oxidative C-H bond additions. The complex cleaves the various sp and sp C-H bonds including those in hexane and methane as inferred from their H/D exchange reactions. The hydroxycyclopentadienyl(nitromethyl)iridium(III) complex was formed when the complex was treated with nitromethane, which highlights this elementary 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).