Encapsulation of vanadium complexes in inorganic or hybrid matrices via the sol-gel method: application to the epoxidation of allylic alcohols

• Autor(a) principal: Pellegrino,Rodolfo B.
• Data de Publicação: 2004
• Outros Autores: Buffon,Regina
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Journal of the Brazilian Chemical Society (Online)
• Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532004000400014
• topic: vanadium; epoxidation; allylic alcohols; sol-gel method

Vanadium complexes have been encapsulated in inorganic (based on hydrolysis/condensation of tetramethylorthosilicate - TMOS) and hybrid matrices (TMOS plus a co-condensation agent) using the sol-gel method. The resulting solids were tested in the epoxidation of allylic alcohols in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant agent at 70 ºC. When the catalyst was based on [VO(salen)], the hybrid matrix led to higher initial turnover frequencies than the inorganic one for all tested alcohols (trans-3-phenyl-2-methyl-2-propen-1-ol, trans-2-hexen-1-ol, cis-2-hexen-1-ol, 1-octen-3-ol), which might be related to its higher pore diameter. Although no vanadium leaching was observed during the catalytic reactions, recycling experiments with the hybrid catalyst and trans-2-hexen-1-ol showed that some loss of vanadium took place at every Soxhlet washing (performed after every run, using CH2Cl2): a total of 1.5 wt.% after three reactions. In four successive runs, keeping the initial molar ratios, conversions decreased from 100% to 85%, 65% and 40% (in 5h).