Microwave-assisted molybdenum-catalysed epoxidation of olefins

• Tipo: Artigo em Revista Científica Internacional
• Data: 2010

Autores

Marta Abrantes (Autor) FEUP; Patrícia Neves (Autor) Outra; Margarida M. Antunes (Autor) Outra; Sandra Gago (Autor) FEUP; Filipe A. Almeida Paz (Autor) FEUP; Alírio E. Rodrigues (Autor) FEUP; Martyn Pillinger (Autor) FEUP; Isabel S. Gonçalves (Autor) FEUP; Carlos M. Silva (Autor) FEUP; Anabela A. Valente (Adaptador) Outra

Revista

Título: Journal of Molecular Catalysis A: Chemical

Páginas: 19-26

ISSN: 1381-1169

Editora: Elsevier B.V.

Indexação

ISI Web of Knowledge - 27 Citações

ISI Web of Science

Scopus - 26 Citações

COMPENDEX

Classificação Científica

FOS: Ciências da engenharia e tecnologias > Engenharia química

CORDIS: Ciências Tecnológicas > Engenharia > Engenharia química

Outras Informações

ID Authenticus: P-003-7Y1

DOI: 10.1016/j.molcata.2009.12.011

Abstract (EN): The performance of CpMo(CO)(3)CH(3) as a catalyst precursor in the epoxidation of cis-cyclooctene and R-(+)-limonene with tert-butylhydroperoxide (TBHP), at 55 degrees C, was investigated for the first time using microwave (MW)-assisted heating, and the results were compared with those obtained using conventional heating with a thermostated oil bath (OB). The reactions were carried out under monophasic (no co-solvent, or with 1,2-dichloroethane, toluene, hexane) or biphasic liquid-liquid (using the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF(4)]) conditions. The heating methods did not affect product selectivity: 100% to cyclooctene oxide, and 93% to limonene oxide (66-72% diastereomeric excess, trans-1,2-(+)-limonene oxide) at 80% limonene conversion. However, the initial reaction rates strongly depend on the applied heating method. The favourable MW effect is essentially due to the faster heating up of the reaction mixture increasing the overall epoxidation rate in the early stage of the heating process, which is supported experimentally by a comparison of (i) the measured temperature vs time curves, (ii) the kinetic data for the MW method with that for the OB method where the reagents and reactor walls are pre-heated (OB-preH method), and (iii) the estimated apparent activation energies and pre-exponential factors for the two olefins using the MW, OB, and OB-preH methods. The crystal structure of the molybdenum tricarbonyl catalyst precursor was unveiled from single-crystal X-ray diffraction studies at 150K.

Idioma: Inglês

Tipo (Avaliação Docente): Científica