화학공학소재연구정보센터
Journal of Molecular Catalysis A-Chemical, Vol.272, No.1-2, 249-257, 2007
Selective oxidation of cyclohexene to di-2-cyclohexenylether by host (nanocavity of zeolite-Y)/guest (manganese(II) complexes with 12-and 14-membered tetraazaz tetraone macrocyclic complexes) nanocomposite materials (HGNM)
Manganese(II) complexes of [12]aneN(4): 1,4,7,1 0-tetraazacyclododecane-2,3,8,9-tetraone; [14]aneN(4): 1,4,8,11-tetraazacyclotetradecane-2,3, 9,10-tetraone; B-ZO2[12]aneN(4): dibenzo-1,4,7,10-tetraazacyclododecane-2,3,8,9-tetraone; B-ZO2[14]aneN(4): dibenzo-1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetraone have been encapsulated in the nanopores of zeolite-Y by the in situ one pot template condensation reaction. Mn(II) complexes with azarnacrocyclic ligand were entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)manganese(II)]; [Mn(N-N)(2)]-NaY; in the supercages of the zeolite, and (ii) in situ condensation of the manganese(II) precursor complex with diethyloxalate. The new host-guest nanocomposite materials (HGNM) have been characterized by FTIR, DRS and UV-vis spectroscopic techniques, XRD and elemental analysis, as well as nitrogen adsorption. These complexes (neat and HGNM) were used for oxidation of cyclohexene with tert-butylhydroperoxide (TBHP) as oxidant in different solvents. Di-2-cyclohexenylether was identified as main product. 2-Cyclohexen-1-one and 2-cyclohexene-1-ol were obtained as minor products. Also it was found [Mn(B-ZO2[12]aneN(4))](2+)-NaY in ethanol had the highest reactivity (84.51%), although the selectivity was 95.10% towards the formation of ether product in methanol. (C) 2007 Elsevier B.V. All rights reserved.