Selective catalytic oxidation of olefins by novel oxovanadium(iv) complexes having different donor ligands covalently anchored on SBA-15: a comparative study

Using a post-synthetic grafting method, mesoporous SBA-15 was functionalized first with aminopropyl silane reagents such as (3-aminopropyl)trimethoxysilane (APTMS) or bis[3-(trimethoxysilyl)propyl]amine (BTMSPA) and then with chlorinated ligands such as 4-(2-chloroacetyl)-3-methyl-1-phenyl-1H-pyrazol- 5(4H)-one (H-AP) or 5-chloromethyl-8-quinolinol hydrochloride (H-HQ). Vanadyl cations [(VO)2+] were then immobilized over functionalized silica samples in order to prepare new oxovanadium(IV) based ‘‘quasihomogeneous’’ catalysts, namely Ia (Ia0 ), Ib (Ib0), and IIa. Alternatively, a preformed oxovanadium(IV) complex such as [VO(AP)2(H2O)] has been immobilized over a previously functionalized SBA-15-NH2 silica support, affording catalyst Ic. Elemental analysis (C, H, N), N2 adsorption–desorption isotherms, FT-IR, 29Si and 13C CP-MAS NMR, XPS, ICP-AES, SEM-EDX and TG-DTG techniques have been used for the full characterization of these materials. Their catalytic properties in the H2O2 promoted oxidation of conjugated olefins like styrene, a-methyl and b-methylstyrene were investigated, in terms of activity, selectivity and recyclability, and compared with that shown by more simple systems prepared by the direct grafting of the vanadyl cation onto SBA-15 (catalyst A) or SBA-15-NH2 (catalyst B). Generally, high activity, selectivity and recyclability (over the first three runs) were shown by all anchored catalysts, with the only exception of A and B systems. A full account of the obtained results, along with insights into the effects due to the different strategies employed for the functionalization of SBA-15 on the properties of final anchored catalysts, are reported.