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    Öğe
    Comparison of Ru(II)-arene complexes containing naphthyl-/ quinolinyl-substituted ligand vis-a-vis structure, spectra and catalytic activity
    (Elsevier, 2024) Turkmen, Gulsah; Cakir, Sinem; Kavukcu, Serdar Batikan; Sahin, Onur; Turkmen, Hayati
    A series of ligands with naphthyl/quinolinyl substituent in their principal molecular framework were synthesised. Their corresponding half -sandwich ruthenium (Ru) complexes ( Ru 1a-b , Ru 2a-b and Ru 3 ) were then successfully generated. The structure of all synthesised compounds was comprehensively elucidated via 1 H and 13 C nuclear magnetic resonance (NMR), elemental analysis and Fourier -transform infrared spectroscopies. Notably, the structural configuration of Ru 3 was delineated via X-ray diffraction. The catalytic efficacy of the Ru complexes was systematically probed in two distinct reactions: 1) transfer hydrogenation (TH) of ketones using 2-propanol as the hydrogen source and 2) reduction of nitroarenes to anilines using sodium tetrahydridoborate as the reducing agent in ethanol, conducted at ambient temperature. Comparative analysis of catalytic yields of the Ru complexes ( Ru 1a-b , Ru 2a-b and Ru 3 ) in both reaction types revealed that Ru 3 delivered superior catalytic performance in both types of reactions. Furthermore, scrutiny of the 1 H NMR spectrum during the TH reaction revealed formation of Ru-hydride species.
  • [ X ]
    Öğe
    N-Alkylation and N-Methylation of Amines with Alcohols Catalyzed by Nitrile-Substituted NHC-Ir(III) and NHC-Ru(II) Complexes
    (Amer Chemical Soc, 2023) Cakir, Sinem; Kavukcu, Serdar Batikan; Sahin, Onur; Gunnaz, Salih; Turkmen, Hayati
    A series of nitrile-modified N-heterocyclic carbene (NHC) complexes of Ir(III) (2a-e) and Ru(II) (3a-d) have been prepared by transmetallation of [IrCp*Cl2]2 and [RuCl2(p-cymene)]2 forming an in situ NHC-Ag complex. The structures of all complexes were characterized by 1H NMR, 13C NMR, and Fourier transform infrared (FT-IR) spectroscopies. And the structures were clearly elucidated by performing X-ray diffraction studies on 2b, 3a, and 3c single crystals. The complexes of NHC- Ir(III) (2a-e) and NHC-Ru(II) (3a-d) were investigated in the N-alkylation reaction of aniline derivatives with benzyl alcohols to form N-benzyl amines and in the N-methylation reaction of aniline derivatives with methanol. Both reactions were performed in solvent-free media. The Ir(III) complexes (2a-e) were found to perform essentially better than similar Ru(II) complexes (3a-d) in the N-alkylation and N-methylation reactions. Among the Ir(III) complexes (2a-e), the best results were obtained with 2b. The catalytic mechanisms of both reactions were revealed by 1H NMR study. Formation of Ir-hydride species was observed for both reactions. This new report provides useful information to evaluate the activity of complexes and the differences in sensitivity between the NHCs.