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

Sofia M. Bruno, Ana C. Gomes, Carla A. Gamelas, Marta Abrantes, M. Conceição Oliveira, Anabela A. Valente, Filipe A. Almeida Paz, Martyn Pillinger, Carlos Jose Romao, Isabel S. Gonçalves

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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(CH 3CN)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.

Original languageEnglish
Pages (from-to)3172-3180
Number of pages9
JournalNew Journal of Chemistry
Volume38
Issue number7
DOIs
Publication statusPublished - 2014

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