2036-39-7Relevant articles and documents
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Bak et al.
, p. 892 (1956)
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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).
H/D exchange processes catalyzed by an iridium-pincer complex
Iluc, Vlad M.,Fedorov, Alexey,Grubbs, Robert H.
scheme or table, p. 39 - 41 (2012/04/10)
A PNP-pincer iridium dihydride performs the H/D exchange between aromatic substrates and tertiary hydrosilanes and D2O or C6D 6. Complete incorporation of deuterium into sterically accessible Car-H and Si-H bonds was observed at a moderate temperature of 80 °C.
