Tetranuclear ruthenium cluster catalysed transfer hydrogenation of α,β-unsaturated aldehydes
- 1 January 1992
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 77-81
- https://doi.org/10.1039/dt9920000077
Abstract
With propan-2-ol as the donor, phosphorus ligand-substituted ruthenium clusters, [Ru4H4(CO)8L4], [L = PBun 3, P(OEt)3, P(OMe)3, PMe3 or PPh3], act as catalysts for the transfer hydrogenation of α, β-unsaturated aldehydes. High selectivities for the reduction of aldehydic functionalities rather than the olefinic ones are observed. Kinetic analyses indicate the existence of a dissociative and a non-dissociative pathway where the latter accounts for more than 99% of the reactions. On the basis of analytical solutions of the rate equations, a computer-assisted error-minimisation procedure yielded the optimum values of the different rate constants. With [2H8]propan-2-ol as the donor, the cluster hydrides do not undergo any isotopic exchange and no isotope effect is observed for the non-dissociative pathway. From Arrhenius plots, activation energies for different ligand-substituted clusters are found to be in the order P(OMe)3 > P(OEt)3 > PBun 3.Keywords
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