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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Novel pyrazolylphosphite- and pyrazolylphosphinite-ruthenium(ii) complexes as catalysts for hydrogenation of
Gershon Amenuvor1, Collins Obuah, Ebbe Nordlander
1Department of Chemistry, University of Johannesburg, PO Box 524, Auckland Park, 2006, South Africa. jdarkwa@uj.ac.za.
Abstract:
The new compounds and potential ligands 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiphenlyphosphinite (L1), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L2), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyl-diethylphosphite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L4) were prepared from the reaction of (3,5-(disubstituted)pyrazol-1H-yl)ethanol and the appropriate phosphine chloride. The phosphinite (L1) and phosphites (L2-L4) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L5) were reacted with [Ru(p-cymene)Cl2]2 to afford the ruthenium(ii) complexes [Ru(p-cymene)Cl2(L1)] (1), [Ru(p-cymene)Cl2(L2)] (2), [Ru(p-cymene)Cl2(L3)] (3), [Ru(p-cymene)Cl2(L4)] (4), and [Ru(p-cymene)Cl2(L5)] (5). All ruthenium complexes were characterized by a combination of NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X-ray crystallography. Complexes 1-5 and [Ru(p-cymene)Cl2(L6)] (6) (prepared from 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L6)) were investigated as catalysts for both transfer and molecular hydrogenation of acetophenone to 1-phenylethanol. At 80 °C the percent conversion of acetophenone in transfer hydrogenation was moderate to high over 10 h (42-87%); for molecular hydrogenation acetophenone, conversions were as high as 98% in 6 h.
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