Please use this identifier to cite or link to this item:
http://hdl.handle.net/10773/19589
Title: | Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of alpha-pinene oxide to campholenic aldehyde |
Author: | Bruno, Sofia M. Gomes, Ana C. Gamelas, Carla A. Abrantes, Marta Conceicao Oliveira, M. Valente, Anabela A. Almeida Paz, Filipe A. Pillinger, Martyn Romao, Carlos C. Goncalves, Isabel S. |
Keywords: | CAMBRIDGE STRUCTURAL DATABASE X-RAY-STRUCTURE ABSOLUTE-CONFIGURATION MOLECULAR-STRUCTURES SANDWICH COMPLEXES CRYSTAL-STRUCTURES RING SLIPPAGE LEWIS-ACIDS MIXED-RING PRECURSORS |
Issue Date: | 2014 |
Publisher: | ROYAL SOC CHEMISTRY |
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. |
Peer review: | yes |
URI: | http://hdl.handle.net/10773/19589 |
DOI: | 10.1039/c4nj00371c |
ISSN: | 1144-0546 |
Publisher Version: | 10.1039/c4nj00371c |
Appears in Collections: | CICECO - Artigos |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde_10.1039c4nj00371c.pdf | 1.43 MB | Adobe PDF |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.