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Design and synthesis of ruthenium(II) OCO pincer type NHC complexes and their catalytic role towards the synthesis of amides

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Abstract

The present contribution describes the synthesis and characterization of a family of robust ruthenium complexes, supported by a tridentate pincer ligand of the type bis-phenolate-N-heterocyclic carbene [ tBu(OCO) 2−] (NHC). Ruthenium(II) complexes (1-3) bearing bis-phenolate-N-heterocyclic carbene ligand were synthesized in good yields by the reaction of imidazolinium proligand (HL) with metal precursors [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) by transmetalation from the corresponding silver carbene complex. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The tridentate nature of the tBu(OCO) 2− ligand as well as some level of steric protection provided by the tBu groups may rationalize the excellent stability of the Ru-Ccarbene bond in the present systems. Moreover, for the explorations of catalytic potential of the synthesized compounds, all the three [Ru-NHC] complexes (1-3) were tested as catalysts for amidation of alcohols with amines. Notably, the complex 1 was found to be very efficient and versatile catalyst towards amidation of a wide range of alcohols with amines.

Three new air-stable Ruthenium(II) complexes bearing bis-phenolate-N-heterocyclic carbene ligand were synthesized and characterized by FT-IR, NMR and ESI-Mass. The catalytic study of these complexes towards amidation of alcohol with amines was conducted. This new protocol is effective for many electronically diverse alcohols and amines, providing corresponding amide derivatives in good to excellent yields.

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Acknowledgements

The authors express their sincere thanks to Science and Engineering Research Board (SERB), Department of Science and Technology, New Delhi, for financial support for this work under the DST FAST TRACK Scheme (No. SR/FT/CS-66/2011). One of the authors (MN) thanks DST-SERB for the award of fellowship.

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  1. Department of Chemistry, Periyar University, Salem, 636 011, Tamil Nadu, India

    MUTHUKUMARAN NIRMALA & PERIASAMY VISWANATHAMURTHI

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  1. MUTHUKUMARAN NIRMALA
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Correspondence to PERIASAMY VISWANATHAMURTHI.

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Supporting Information

Representative NMR (1H, 13C, 31P) and ESI-MS spectra of ligand and complexes (figures S1-S10), detailed experimental procedure, spectral data and selected 1H and 13C NMR spectra for amide products (figures S11-S18) are given in the supporting information available at www.ias.ac.in/chemsci.

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NIRMALA, M., VISWANATHAMURTHI, P. Design and synthesis of ruthenium(II) OCO pincer type NHC complexes and their catalytic role towards the synthesis of amides. J Chem Sci 128, 9–21 (2016). https://doi.org/10.1007/s12039-015-0997-5

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