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.
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 CuII 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.
Silva
Telma F S
TF
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisboa, Portugal.
Mishra
Gopal S
GS
da Silva
M Fátima Guedes
MF
Wanke
Riccardo
R
Martins
Luísa M D R S
LM
Pombeiro
Armando J L
AJ
D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003510:Cyclohexanes / Q000737:chemistry*; D006860:Hydrogen Bonding; D008698:Mesylates / Q000737:chemistry*; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011720:Pyrazoles / Q000737:chemistry*
C551362:2,2,2-tris(1-pyrazolyl)ethanol; C551363:2,2,2-tris(1-pyrazolyl)ethyl methanesulfonate; D056831:Coordination Complexes; D003510:Cyclohexanes; D008698:Mesylates; D011720:Pyrazoles; C506365:Cyclohexane; D003300:Copper; C029892:cupric chloride