Molybdenum(II) Diiodo-Tricarbonyl Complexes Containing Nitrogen Donor Ligands as Catalyst Precursors for the Epoxidation of Methyl Oleate

resumo

The molybdenum(II) tricarbonyl complexes [Mo(CO)(3)I2L (n) ] (n = 1, L = 2,2'-bipyridine, 4,4'-di-tert-butyl-2,2'-bipyridine; n = 2, L = pyridine, 4-tert-butylpyridine) have been examined as catalyst precursors for the epoxidation of the biorenewable olefin methyl oleate with tert-butylhydroperoxide. In situ oxidative decarbonylation of the precursors gives highly active and selective molybdenum(VI) catalysts, which were identified as the one-dimensional molybdenum oxide/bipyridine polymer [MoO3(2,2'-bipyridine)], octanuclear [Mo8O24(4,4'-di-tert-butyl-2,2'-bipyridine)(4)], and the pyridinium beta-octamolybdates (LH)(4)[Mo8O26] for L = pyridine or 4-tert-butylpyridine.

palavras-chave

EPOXIDIZED SOYBEAN OIL; TERT-BUTYL HYDROPEROXIDE; UNSATURATED FATTY-ACIDS; OLEFIN EPOXIDATION; TUNGSTEN COMPLEXES; VEGETABLE-OILS; ETA(5)-CYCLOPENTADIENYL MOLYBDENUM; CYCLOALKYL MOIETIES; BETA-OCTAMOLYBDATE; CRYSTAL-STRUCTURE

categoria

Chemistry

autores

Gamelas, CA; Neves, P; Gomes, AC; Valente, AA; Romao, CC; Goncalves, IS; Pillinger, M

nossos autores

agradecimentos

We are grateful to the Fundacao para a Ciencia e a Tecnologia (FCT), QREN, FEDER, COMPETE, the European Union and the Associate Laboratory CICECO (Pest-C/CTM/LA0011/2011) for continued support and funding. The FCT is acknowledged for a post-doctoral grant to PN (SFRH/BPD/73540/2010). The NMR spectrometers are part of The National NMR Network (REDE/1517/RMN/2005), supported by POCI 2010 and the FCT.

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