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Sequential Oxidation and C−H Bond Activation at a Gallium(I) Center
Author(s) -
Kassymbek Aishabibi,
Vyboishchikov Sergei F.,
Gabidullin Bulat M.,
Spasyuk Denis,
Pilkington Melanie,
Nikonov Georgii I.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201913028
Subject(s) - chemistry , gallium , adduct , steric effects , pyridine , cleave , monomer , ligand (biochemistry) , oxide , photochemistry , medicinal chemistry , polymer chemistry , stereochemistry , inorganic chemistry , organic chemistry , enzyme , biochemistry , receptor , polymer
In situ oxidation of the Ga I compound NacNacGa by either N 2 O 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 abstract protons from nearby C−H bonds, even for sp 2 ‐hybridized carbon centers. Aliphatic amines do not enter this reaction for kinetic reasons, presumably because of the unfavorable sterics.