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authors |
Bruno, SM; Gomes, AC; Gamelas, CA; Abrantes, M; Oliveira, MC; Valente, AA; Paz, FAA; Pillinger, M; Romao, CC; Goncalves, IS |
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nationality |
International |
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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. |
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publisher |
ROYAL SOC CHEMISTRY |
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issn |
1144-0546 |
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year published |
2014 |
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volume |
38 |
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issue |
7 |
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beginning page |
3172 |
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ending page |
3180 |
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digital object identifier (doi) |
10.1039/c4nj00371c |
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web of science category |
Chemistry, Multidisciplinary |
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subject category |
Chemistry |
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unique article identifier |
WOS:000338117900060
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