Labelling Studies to Determine Product Formation from Reactions of CO and Hydrogen Catalysed by Ru Clusters and Rh Complexes

Autor: Martin J. Lofthouse, Evert J. Ditzel, David J. Cole-Hamilton, Andrew J. Poole
Rok vydání: 2006
Předmět:
Zdroj: Journal of Cluster Science. 17:27-45
ISSN: 1572-8862
1040-7278
Popis: Reaction of CO with hydrogen in the presence of [Ru3(CO)12], KI and N-methylpyrrolidone produces small amounts of methanol under mild conditions. Using D2 the methanol is CD3OD confirming that it is a product of CO hydrogenation. In the presence of added H2O, CH x D1-y OH/D (y=0–3) are produced. Carrying out the same reaction in the presence of MeI water and RhCl3·xH2O (x=3–4) produces ethanoic acid in a slow reaction which continues for at least 64 h. The effects of different reaction parameters are discussed and labelling using 13CH3I shows that some of the ethanoic acid originates from sources other than MeI whilst labelling with D2, CD3I, and/or D2O suggest that some originates from CO and H2. Electrospray mass spectrometry and high pressure infra-red spectroscopic studies show that the main species present in catalytic solutions are [HRu3(CO)11]−, [HRu4(CO)13]− and [Ru(CO)3I3]− for methanol carbonylation, [Ru(CO)3I3]− and [RhI2(CO)2]− for ethanoic acid production. A reaction carried out in the absence of [Ru3(CO)12] gave similar results to a reaction in which it was added, suggesting that the entire process may be catalysed by rhodium complexes alone.
Databáze: OpenAIRE
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