An attractive route to transamidation catalysis: Facile synthesis of new o-aryloxide-N-heterocyclic carbene ruthenium(II) complexes containing trans triphenylphosphine donors

• Published in: Journal of molecular catalysis. A, Chemical Vol. 403; pp. 15 - 26
• Main Authors: Nirmala, Muthukumaran, Prakash, Govindan, Viswanathamurthi, Periasamy, Malecki, Jan Grzegorz
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-07-2015
• Subjects: [Ru–NHC] complexes; Imidazolium proligands; Transamidation; Transmetallation; X-ray diffraction; [Ru–NHC] complexes; X-ray diffraction; Imidazolium proligands; Transamidation; Transmetallation
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2015.03.015

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•New o-aryloxide-N-heterocyclic carbene ruthenium(II) catalysts have been synthesized and characterized.•X-ray studies revealed an octahedral geometry of the new complexes.•The new catalysts catalyze the transamidation of carboxamides with amines effectively.
Well-defined robust ruthenium(II) complexes 3a–d bearing o-aryloxide-N-heterocyclic carbene ligands with different wingtip substituents (3a (R=Me), 3b (R=Ph), 3c (R=iPr) and 3d (R=Mes)) in the imidazole ring were synthesized in good yields by the reaction of imidazolium proligands with metal precursor [RuHCl(CO)(PPh3)3] by transmetallation from the corresponding silver carbene complexes. All the Ru(II)–NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. The molecular structure of the complex 3a was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted octahedral geometry. In order to explore the catalytic potential of the synthesized complexes, all the four [Ru–NHC] complexes [3a–d] were tested as catalysts for transamidation of carboxamides with amines. Notably, the complex 3a was found to be very efficient and versatile catalyst toward transamidation of a wide range of amides with amines.