resumo
Methoxysilane Schiff-base pentacoordinate metal complexes, Le. Fe[Sal(PMeO-Si)DPTA], Ni[Sal(PMeO-Si)DPTA] and Mn[Sal(PMeO-Si)DPTA], were synthesized and single site covalently anchored into the uniform porous texture of HMS (2-10 nm size) via condensation process. The correspondent supported catalysts (4.a, 4.b and 4.c, respectively) were characterized by FT-IR, SEM/EDS, XRD, TG, EPR and AAS analysis. In the catalytic tests, they showed high efficiency in the selective oxidation of cyclohexane using molecular O-2 (overall conversion 40.7% with Cat. 4.a, 29.5% with Cat. 4.b and 26.2% with Cat. 4.c) under relatively mild condition in batch reactor. The Cat.4.a system (HMS/3.a) exhibits highest TONs ca. 4.2 x 10(3) with good selectivity ca. 70% (48% ketone selectivity). The reaction mechanism involves free radicals, as it was proved by the addition of PPh3. Finally, these supported catalysts could be reuse up to several catalytic cycles. (C) 2013 Elsevier B.V. All rights reserved.
palavras-chave
MODIFIED SILICA-GEL; H BOND ACTIVATION; CYCLOHEXANE OXIDATION; MOLECULAR-OXYGEN; HYDROCARBON OXIDATION; PEROXIDATIVE OXIDATION; ZEOLITE-Y; MCM-41; COPPER(II); DIOXYGEN
categoria
Chemistry
autores
Machado, K; Tavares, PB; Mishra, GS
nossos autores
Gopal Shankar Mishra
Bolseiro de pós-DoutoramentoGrupos
agradecimentos
This work is financially supported by the Fundacao para a Ciencia e Tecnologia (FCT) of Portugal through projects: PTDC/EQU-ERQ/110825/2009, CQVR/PEst-C/QUI/UI0616/2011 and