Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of alpha-pinene oxide to campholenic aldehyde
authors Bruno, SM; Gomes, AC; Gamelas, CA; Abrantes, M; Oliveira, MC; Valente, AA; Paz, FAA; Pillinger, M; Romao, CC; Goncalves, IS
nationality International
journal NEW JOURNAL OF CHEMISTRY
keywords CAMBRIDGE STRUCTURAL DATABASE; X-RAY-STRUCTURE; ABSOLUTE-CONFIGURATION; MOLECULAR-STRUCTURES; SANDWICH COMPLEXES; CRYSTAL-STRUCTURES; RING SLIPPAGE; LEWIS-ACIDS; MIXED-RING; PRECURSORS
abstract The complex [{(eta(5)-Ind)Mo(CO)(2)(mu-CI)(2)] (1) has been tested for the industrially relevant catalytic isomerisation of CL-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 degrees C or 30 min at 35 degrees 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 [{(eta(5)-Ind)Mo(CO)(2)(mu-CI)(2)] (2) (obtained after dissolution of 1 in acetonitrile) is reported.
publisher ROYAL SOC CHEMISTRY
issn 1144-0546
year published 2014
volume 38
issue 7
beginning page 3172
ending page 3180
digital object identifier (doi) 10.1039/c4nj00371c
web of science category Chemistry, Multidisciplinary
subject category Chemistry
unique article identifier WOS:000338117900060
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journal impact factor (jcr 2016): 3.269
5 year journal impact factor (jcr 2016): 3.103
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