133544-10-2Relevant academic research and scientific papers
Half-sandwich ruthenium(II) complexes containing 4-substituted aniline derivatives: structural characterizations and catalytic properties in transfer hydrogenation of ketones
Sad?k, Mean,Karabork, Muharrem,Sahin, Irfan,Kose, Muhammet
, p. 457 - 464 (2021)
Four half-sandwich Ru(II) complexes (1)–(4) with the general formulae [Ru(η6-p-cymene)(L)Cl2] were synthesized by the reaction of one equivalent of the Ru(II) p-cymene dimer with two equivalents of a p-substituted aniline derivative L (where L is p-methyl, p-isopropyl, p-methoxy, or p-hydroxy aniline). The structures of complexes (2)–(4) were determined by single-crystal X-ray diffraction studies. The structural analysis revealed piano-stool geometry at the Ru(II) ions which are coordinated to the η6-p-cymene, two chloride anions and the amine group of the aniline ligand. In the structure of (2)–(4), the coordinated chloride ions make intermolecular hydrogen bonding with the –NH2 group of an adjacent molecules (NH–Cl) resulting in hydrogen bond networks. The catalytic activities of the complexes in transfer hydrogenation of acetophenone were studied. Complex [Ru(η6-p-cymene)(p-methylaniline)Cl2] (1) showed the best catalytic performance in the transfer hydrogenation of acetophenone. The presence and positions of methyl and bromide groups on the acetophenone have an impact on the catalytic activity in transfer hydrogenation properties of the complex (1). Moreover, catalytic activity of the complex (1) is significantly higher in the transfers hydrogenation of cyclohexanone than 2-hexanone.
C?H Bond Activation/Arylation Catalyzed by Arene–Ruthenium–Aniline Complexes in Water
Binnani, Chinky,Tyagi, Deepika,Rai, Rohit K.,Mobin, Shaikh M.,Singh, Sanjay K.
supporting information, p. 3022 - 3031 (2016/11/13)
Water-soluble arene–ruthenium complexes coordinated with readily available aniline-based ligands were successfully employed as highly active catalysts in the C?H bond activation and arylation of 2-phenylpyridine with aryl halides in water. A variety of (hetero)aryl halides were also used for the ortho-C?H bond arylation of 2-phenylpyridine to afford the corresponding ortho- monoarylated products as major products in moderate to good yields. Our investigations, including time-scaled NMR spectroscopy and mass spectrometry studies, evidenced that the coordinating aniline-based ligands, having varying electronic and steric properties, had a significant influence on the catalytic activity of the resulting arene–ruthenium–aniline-based complexes. Moreover, mass spectrometry identification of the cycloruthenated species, {(η6-arene)Ru(κ2-C,N-phenylpyridine)}+, and several ligand-coordinated cycloruthenated species, such as [(η6-arene)Ru(4-methylaniline)(κ2-C,N-phenylpyridine)]+, found during the reaction of 2-phenylpyridine with the arene–ruthenium–aniline complexes further authenticated the crucial roles of these species in the observed highly active and tuned catalyst. At last, the structures of a few of the active catalysts were also confirmed by single-crystal X-ray diffraction studies.
