resumo
The new coordination polymer formulated as [Et3SnVO3] (1) has been synthesized and shown by a combined single-crystal and synchrotron powder X-ray diffraction structural analysis, supported by solid-state NMR, to possess a three-dimensional network structure with the sodalite topology, formed by tetravanadate polyanions, [V4O12](4-), that are linked by Et3Sn+ spacers. The catalytic versatility of compound 1 for liquid phase organic reactions was demonstrated by applying it for the epoxidation of olefins, the oxidative dehydrogenation of alcohols, and the oxidation of benzyl alcohol to benzaldehyde and benzoic acid, using tert-butyl hydroperoxide (TBHP) as oxidant. Compound 1 acts a solid reservoir for soluble, catalytically active species, which promote high selectivities to the epoxide and carbonyl (aldehyde/ketone/acid) products. The epoxidation activity compares favorably with those reported for other organotin molybdate, tungstate and vanadate coordination polymers, and is superior to that displayed by the starting materials used for its synthesis (Et3SnBr and NH4VO3) and the metavanadate NBu4VO3.
palavras-chave
TRIAZOLYLMOLYBDENUM(VI) OXIDE HYBRIDS; MONOORGANOTIN-POLYOXOMETAL-COMPOUNDS; OXOMOLYBDATE COORDINATION POLYMERS; CRYSTAL-STRUCTURE; HYDROGEN-PEROXIDE; OLEFIN EPOXIDATION; COMPLEXES; VANADIUM; MOLYBDENUM; DIFFRACTION
categoria
Chemistry
autores
Gomes, AC; Antunes, MM; Abrantes, M; Valente, AA; Paz, FAA; Goncalves, IS; Pillinger, M
nossos autores
Ana Catarina Costa Gomes Alves
Investigador Auxiliar
Anabela Tavares Aguiar Valente
Investigador Principal
Filipe Alexandre Almeida Paz
Investigador Principal
Isabel Maria de Sousa Gonçalves
Professor associado
Maria Margarida Feitor Pintão Moreno Antunes
Investigador Júnior
Martyn Pillinger
Investigador JúniorGrupos
1 - nanomateriais inorgânicos funcionais e híbridos orgânico-inorgânico
4 - biorrefinarias, materiais de origem biológica e reciclagem
agradecimentos
This work was developed in the scope of the project (Associate Laboratory) CICECO-Aveiro Institute of Materials - POCI-01-0145-FEDER-007679 [FCT (Fundacao para a Ciencia e a Tecnologia) ref. UID/CTM/50011/2013], financed by national funds through the FCT/MEC and when applicable co-financed by FEDER (Fundo Europeu de Desenvolvimento Regional) under the PT2020 Partnership Agreement. We wish to thank the European Synchrotron Radiation Facility (ESRF), Grenoble, France for granting access to the Swiss-Norwegian beam line BM01b through the approved project CH-3994. The FCT and the European Union are acknowledged for post-doctoral grants to A.C.G. (SFRH/BPD/108541/2015) and M.M.A. (SFRH/BPD/89068/2012), co-funded by MCTES and the European Social Fund through the program POPH of QREN.