MUTHUKUMARAN NIRMALA
Articles written in Journal of Chemical Sciences
Volume 128 Issue 1 January 2016 pp 9-21 Regular Articles
Muthukumaran Nirmala Periasamy Viswanathamurthi
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 (
Volume 128 Issue 11 November 2016 pp 1725-1735 Regular Article
MUTHUKUMARAN NIRMALA PERIASAMY VISWANATHAMURTHI
A series of four imidazolium salts was synthesized by the reaction of 2-bromopyridine with 1- substituted imidazoles. These imidazolium salts (1a–d) were successfully employed as ligand precursors for the syntheses of new ruthenium(II) complexes bearing neutral bidentate ligands of N-heterocyclic carbene and pyridine donor moiety. The NHC-ruthenium(II) complexes (3a–d) were synthesized by reacting the appropriately substituted pyridine-functionalized N-heterocyclic carbenes with Ag₂O forming the NHC–silver bromide in situ followed by transmetalation with [RuHCl(CO)(PPh₃)₃]. The new complexes were characterized by elemental analyses and spectroscopy (IR, UV-Vis, ¹H, ¹³C, ³¹P-NMR) as well as ESI mass spectrometry. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The complexes were shown to be efficient catalysts for the one-pot conversion of various aldehydes to their corresponding primary amides with good to excellent isolated yields using NH₂OH.HCl and NaHCO₃. The effects of solvent, base, temperature, time and catalyst loading were also investigated. A broad range of amides were successfully synthesized with excellent isolated yields using the above optimized protocol. Notably, the complex 3a was found to be a very efficient and versatile catalyst towards amidation of a wide range of aldehydes.
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