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Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde.
- Source :
- New Journal of Chemistry; 2014, Vol. 38 Issue 7, p3172-3180, 9p
- Publication Year :
- 2014
-
Abstract
- The complex [{(η<superscript>5</superscript>-Ind)Mo(CO)<subscript>2</subscript>(μ-Cl)}<subscript>2</subscript>] (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)<subscript>2</subscript>(CH<subscript>3</subscript>CN)<subscript>n</subscript>]<superscript>+</superscript>. The crystal structure of the ring-slipped dicarbonyl complex [(η<superscript>3</superscript>-Ind)Mo(CO)<subscript>2</subscript>Cl(CH<subscript>3</subscript>CN)<subscript>2</subscript>] (2) (obtained after dissolution of 1 in acetonitrile) is reported. [ABSTRACT FROM AUTHOR]
- Subjects :
- PINENE
CHROMIUM group
MOLYBDENUM
ISOMERIZATION
TERPENES
Subjects
Details
- Language :
- English
- ISSN :
- 11440546
- Volume :
- 38
- Issue :
- 7
- Database :
- Complementary Index
- Journal :
- New Journal of Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 100402916
- Full Text :
- https://doi.org/10.1039/c4nj00371c