C−H Bond Activation/Arylation Catalyzed by Arene–Ruthenium–Aniline Complexes in Water

Abstract

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. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim