Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 31, Pages 5000-5010Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201200733
Keywords
Metallocenes; Structure elucidation; Isomerization; Phosphane ligands; Ruthenium
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Funding
- Grant Agency of Charles University in Prague [69309]
- Ministry of Education, Youth and Sports of the Czech Republic [MSM0021620857]
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Phosphanylferrocenecarboxamide Ph(2)PfcCONHCH(2)-CH2OH (1, fc = ferrocene-1,1'-diyl) and its newly synthesized congeners, Ph(2)PfcCONHCH(CH2OH)(2) (2) and Ph(2)PfcCONHC(CH2OH)(3) (3), were converted to a series of (eta(6)-arene)ruthenium complexes [(eta(6)-arene)RuCl2(L-kappa P)] 57, where arene is benzene, p-cymene, and hexamethylbenzene and L = 13. All compounds were characterized by multinuclear NMR and IR spectroscopy, by mass spectrometry, and by elemental analysis. The molecular structures of 2, 3, 3O (a phosphane oxide resulting from the oxidation of 3), 5c center dot CH2Cl2, and 6c center dot Et2O were determined by single-crystal X-ray diffraction analysis. The ruthenium complexes were further evaluated as catalysts in the redox isomerization of allyl alcohols to carbonyl compounds. Complex [(eta(6)-p-cymene)RuCl2(1-kappa P)] (5b) proved to be a particularly attractive catalyst, being both readily available and catalytically active. Substrates with unsubstituted double bonds were cleanly isomerized with this catalyst in 1,2-dichloroethane (0.5 mol-% Ru, 80 degrees C), whereas for those bearing substituents at the double bond (particularly in the position closer to the OH group) lower conversions and selectivities were achieved. A similar trend was noted when pure water was used as the solvent, except that the best results (complete conversion with 2 mol-% Ru) were seen for 1,3-diphenylallyl alcohol, the most hydrophobic substrate.
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