Tetracopper(II) Cores Driven by an Unexplored Trifunctional Aminoalcohol Sulfonic Acid for Mild Catalytic C–H Functionalization of Alkanes

Catalysts

TiagoA. Fernandes¹  MarinaV. Kirillova¹  InêsF. M. Costa¹  Vânia André¹  AlexanderM. Kirillov¹ 

[1] Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal;

关键词: copper;    homogeneous catalysis;    cycloalkanes;    propane;    oxidation;    carboxylation;    C−H functionalization;    bioinspired systems;   

DOI  :  10.3390/catal9040321

来源: DOAJ

【 摘 要 】

Three new tetracopper(II) coordination compounds were easily generated from Cu(NO₃)₂, a trifunctional aminoalcohol sulfonic acid (H₃bes, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid) as a principal building block, and a benzene carboxylic acid as a supporting ligand (i.e., benzoic (Hba), 4-hydroxybenzoic (Hfba), or 3-hydroxybenzoic (Hthba) acid). The obtained microcrystalline products, [Cu₄(µ-Hbes)₃(µ-H₂bes)(µ-L)]·2H₂O (L = ba⁻ (1), fhba⁻ (2), and thba⁻ (3)), were fully characterized by FTIR (Fourier-transform infrared spectroscopy), elemental analysis, ESI-MS (Electrospray Ionisation Mass Spectrometry), and single-crystal X-ray diffraction methods. Compounds 1–3 were applied as effective homogeneous catalysts in the oxidative C−H functionalization of alkanes (cycloalkanes and propane). Two different model reactions were explored: (1) mild oxidation of alkanes with hydrogen peroxide to give alcohols and ketones, and (2) mild carboxylation of alkanes with carbon monoxide, water, and potassium peroxodisulfate to give carboxylic acids. For these reactions, effects of different parameters, as well as mechanistic and selectivity characteristics, were studied.

【 授权许可】

Unknown