Cakir, SinemKavukcu, Serdar BatikanSahin, OnurGunnaz, SalihTurkmen, Hayati2025-03-232025-03-2320232470-1343https://doi.org/10.1021/acsomega.2c06341https://hdl.handle.net/11486/5945A 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.eninfo:eu-repo/semantics/openAccessReductive AminationRuthenium(Ii) ComplexesTransfer HydrogenationSecondary AlcoholsAromatic-AminesIonic LiquidsAryl HalidesNhc LigandsEfficientDehydrogenationArticle10.1021/acsomega.2c06341368166362-s2.0-85147588912Q1WOS:000927314400001Q2