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Synthesis, structural characterisation and catalytic application of dichloro(η 6-p-cymene){diphenyl(3-methyl-2-indolyl)phosphine}ruthenium(II) in the transfer hydrogenation of ketones

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Abstract

The synthesis and investigation of ruthenium complexes containing the relatively unexplored ligand, diphenyl-2-(3-methyl)indolylphosphine, is presented herein. The complexes [RuCl2{PPh2(C9H8N)}3], [Ru2(μ-Cl)3(Cl)(MeCN){PPh2(C9H8N)}4] and [RuCl2(η 6-p-cymeme){PPh2(C9H8N)}] have been studied. Single crystals of the latter two complexes have been prepared and investigated by X-ray crystallography. A detailed examination of [RuCl2(η 6-p-cymeme){PPh2(C9H8N)}] has been carried out. This complex was found to be an active catalyst in the catalytic transfer hydrogenation of ketones.

Graphical Abstract

The complex, [RuCl2(η 6-p-cymeme){PPh2(C9H8N)}], was synthesised and fully characterised by spectroscopic, analytical and structural methods. The complex was also found to be an active catalyst in the transfer hydrogenation of ketones.

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Fig. 1
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Notes

  1. Mixtures containing [RuCl2(COD)]n and 2 equivalents of L were heated to reflux in MeCN for several days. The 31P{1H} NMR spectrum of the reaction mixture revealed mostly free ligand with only traces of a new species at 13.9 ppm (<10 %) which was likely to correspond to the target product, RuCl2(COD)L. The lack of reactivity is presumably due to the inability of L to break the chloride bridges in the polymeric starting material. Due the this lack of reactivity, the route was not further explored.

  2. We found that removal of the solvents by evaporation according to standard methods led to significant variations in the ratio of substrate to product. These variations were significant particularly in the case of cyclohexanone and cyclohexanol. Accordingly, the reaction solvent was not removed, and a solvent suppression 1H NMR experiment was performed on the reaction mixture. This method was calibrated, at several designated ratios, by measuring the relative integration of substrates to products under the same concentrations as used for the catalytic reactions. Furthermore, all flasks were thoroughly cleaned with aqua regia and subsequently thoroughly washed with water and acetone prior to performing the catalytic tests.

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Acknowledgments

The authors thank the Royal Society for a Royal Society Dorothy Hodgkin Research Fellowship for GRO and Johnson Matthey for the generous loan of ruthenium salts.

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  1. The School of Chemistry, Cantock’s Close, Bristol, UK

    Yu-Ying Kuo, Mairi F. Haddow, Ashley L. Jamieson & Gareth R. Owen

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  1. Yu-Ying Kuo
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Correspondence to Gareth R. Owen.

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Kuo, YY., Haddow, M.F., Jamieson, A.L. et al. Synthesis, structural characterisation and catalytic application of dichloro(η 6-p-cymene){diphenyl(3-methyl-2-indolyl)phosphine}ruthenium(II) in the transfer hydrogenation of ketones. Transition Met Chem 38, 641–648 (2013). https://doi.org/10.1007/s11243-013-9732-6

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