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Abstract(s)
The complex [{(Z5-Ind)Mo(CO)2(m-Cl)}2] (1) has been tested for the industrially relevant catalytic isomerisation
of a-pinene oxide (PinOx) to campholenic aldehyde (CPA) in the liquid phase. PinOx conversion and CPA
selectivity are strongly influenced by the solvent employed. Complete conversion of PinOx was achieved
within 1 min at 55 1C or 30 min at 35 1C using 1,2-dichloroethane as solvent, giving CPA in 68% yield.
Other products included trans-carveol, iso-pinocamphone and trans-pinocarveol. The stability of 1 under
the reaction conditions used was investigated by using FT-IR spectroscopy and electrospray ionisation
mass spectrometry (ESI-MS) to characterise recovered solids. In the presence of air/moisture 1 undergoes
oxidative decarbonylation upon dissolution to give oxomolybdenum species that are proposed to include
a tetranuclear oxomolybdenum(V) complex. Conversely, ESI-MS studies of 1 dissolved in dry acetonitrile
show mononuclear species of the type [IndMo(CO)2(CH3CN)n]+. The crystal structure of the ring-slipped
dicarbonyl complex [(Z3-Ind)Mo(CO)2Cl(CH3CN)2] (2) (obtained after dissolution of 1 in acetonitrile) is
reported.
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Citation
Bruno, S., Gomes, A., Gamelas, C., Abrantes, M., Oliveira, M. C., Valente, A., Almeida-Paz, F. …Gonçalves, I. (2013). Application of an Indenyl Molybdenum Dicarbonyl Complex in the Isomerisation of α-Pinene Oxide to Campholenic Aldehyde. New Journal of Chemistry, 38, pp. 3172-3180. doi: 10.1039/C4NJ00371C