Cu-II complexes bearing the 2,2,2-tris(1-pyrazolyl)ethanol or 2,2,2-tris(1-pyrazolyl)ethyl methanesulfonate scorpionates. X-Ray structural characterization and application in the mild catalytic peroxidative oxidation of cyclohexane
authors Silva, TFS; Mishra, GS; da Silva, MFG; Wanke, R; Martins, LMDRS; Pombeiro, AJL
nationality International
journal DALTON TRANSACTIONS
keywords COPPER TRIETHANOLAMINE COMPLEXES; HYDROGEN-PEROXIDE; ALKANE OXIDATION; VANADIUM COMPLEXES; RHENIUM COMPLEXES; METAL-COMPLEXES; ACETIC-ACID; BIS(MALTOLATO)OXOVANADIUM COMPLEXES; EFFICIENT CATALYSTS; MOLECULAR-OXYGEN
abstract Reactions between CuCl2 and the functionalized scorpionate 2,2,2-tris(1-pyrazolyl)ethanol HOCH2C(pz)(3) 1 (pz = pyrazolyl) or 2,2,2-tris(1-pyrazolyl)ethyl methanesulfonate CH3SO2OCH2C(pz)(3) 2 yield the corresponding water soluble Cu-II complexes [CuCl2{HOCH2C(pz)(3)}](3) or [CuCl2{CH3SO2OCH2C(pz)(3)}](2) 4. In 3 the scorpionate ligand shows the typical N,N,N-coordination mode, whereas in the dinuclear complex 4 it binds the metal as a bidentate species. Compounds 1-4 have been characterized by IR, far-IR, elemental analysis and (for 2-4) single crystal X-ray diffraction. The new scorpionate complexes 3 and 4 are shown to act as catalyst precursors for the peroxidative oxidation of cyclohexane to cyclohexanol (main product) and cyclohexanone, under mild conditions (at room temperature and using an aqueous solution of H2O2) reaching TON values up to 186 in NCMe/H2O. Their hydrosolubility allows them to operate also in pure aqueous media (without any organic solvent, although less effectively), a rare feature of significance towards a green alkane oxidation process.
publisher ROYAL SOC CHEMISTRY
issn 1477-9226
year published 2009
issue 42
beginning page 9207
ending page 9215
digital object identifier (doi) 10.1039/b911990f
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000270973800019
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