Details

Autor(en) / Beteiligte

• Kassymbek, Aishabibi
• Vyboishchikov, Sergei F.
• Gabidullin, Bulat M.
• Spasyuk, Denis
• Pilkington, Melanie
• Nikonov, Georgii I.

Titel

Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center

Ist Teil von

• Angewandte Chemie International Edition, 2019-12, Vol.58 (50), p.18102-18107

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2019

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• In situ oxidation of the GaI compound NacNacGa by either N2O or pyridine oxide results in the generation of a labile monomeric oxide, NacNacGa(O), which can easily cleave the C−H bonds of aliphatic and aromatic substrates featuring good donor sites. The products of this reaction are gallium organyl hydroxides. DFT calculations show that these reactions start with the formation of NacNac‐Ga(O)(L) adducts, the oxo ligand of which can easily protons from nearby C−H bonds, even for sp2‐hybridized carbon centers. Aliphatic amines do not enter this reaction for kinetic reasons, presumably because of the unfavorable sterics. NacNac! Who′s there? In situ oxidation of the GaI compound 1 results in the transient monomeric oxo derivative NacNacGa=O, which adds to C−H bonds of a variety of substrates featuring hard donor sites. Density‐functional calculations are also presented.