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Issue 7, 2014
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Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

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Abstract

The complex [{(η5-Ind)Mo(CO)2(μ-Cl)}2] (1) has been tested for the industrially relevant catalytic isomerisation of α-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 °C or 30 min at 35 °C 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 [(η3-Ind)Mo(CO)2Cl(CH3CN)2] (2) (obtained after dissolution of 1 in acetonitrile) is reported.

Graphical abstract: Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

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Publication details

The article was received on 12 Mar 2014, accepted on 15 Apr 2014 and first published on 24 Apr 2014


Article type: Paper
DOI: 10.1039/C4NJ00371C
Citation: New J. Chem., 2014,38, 3172-3180
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    Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

    S. M. Bruno, A. C. Gomes, C. A. Gamelas, M. Abrantes, M. C. Oliveira, A. A. Valente, F. A. Almeida Paz, M. Pillinger, C. C. Romão and I. S. Gonçalves, New J. Chem., 2014, 38, 3172
    DOI: 10.1039/C4NJ00371C

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