Issue 10, 2015

Half-sandwich Ru(η6-C6H6) complexes with chiral aroylthioureas for enhanced asymmetric transfer hydrogenation of ketones – experimental and theoretical studies

Abstract

The reactions of [RuCl26-C6H6)]2 with chiral aroylthiourea ligands yielded pseudo-octahedral half-sandwich “piano-stool” complexes. All the Ru(II) complexes were characterized by analytical and spectral (UV-visible, FT-IR, 1H NMR and 13C NMR) studies. The molecular structures of the ligands (L2 and L4) and the complexes (2, 4 and 5) were confirmed by single crystal XRD. All the complexes were successfully screened as catalysts for the asymmetric transfer hydrogenation (ATH) of ketones using 2-propanol as the hydrogen source in the presence of KOH. The ATH reactions proceeded with excellent yields (up to 99%) and very good enantioselectivity (up to 99% ee). The scope of the present catalytic system was extended to substituted aromatic ketones and few hetero-aromatic ketones. Density functional theory (DFT) calculations predicted non-classical, concerted transition states for the ATH reactions. The catalytic activity of Ru–benzene complexes toward asymmetric reduction of ketones was significantly higher compared to that of p-cymene complex analogues. Such enhanced efficiency and product selectivity of Ru–benzene complexes compared to those of Ru–p-cymene complexes were rationalized by the computational study.

Graphical abstract: Half-sandwich Ru(η6-C6H6) complexes with chiral aroylthioureas for enhanced asymmetric transfer hydrogenation of ketones – experimental and theoretical studies

Supplementary files

Article information

Article type
Paper
Submitted
26 May 2015
Accepted
03 Jul 2015
First published
03 Jul 2015

Catal. Sci. Technol., 2015,5, 4790-4799

Half-sandwich Ru(η6-C6H6) complexes with chiral aroylthioureas for enhanced asymmetric transfer hydrogenation of ketones – experimental and theoretical studies

M. Mary Sheeba, S. Preethi, A. Nijamudheen, M. Muthu Tamizh, A. Datta, L. J. Farrugia and R. Karvembu, Catal. Sci. Technol., 2015, 5, 4790 DOI: 10.1039/C5CY00774G

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