Hetero-Bimetallic Complexes Based on an Anthyridine Ligand Preparation and Catalytic Activity
Organometallics(2019)
摘要
Complexation of anthyridine-based ligand L with [(η6-cymene)RuCl2]2, [Cp*RhCl2]2, and [Cp*IrCl2]2 yielded a mononuclear complex: [(N,N-L)Ru(η6-cymene)Cl]Cl (1), [(N,N-L)Rh(Cp*)Cl]Cl (2), and [(N,N-L)Ir(Cp*)Cl]Cl (3), respectively [L = 5-phenyl-2,8-di-2-pyridinylanthyridine]. Upon treatment with (CH3CN)PdCl2, complexes 1–3 underwent o-metalation to yield heterobimetallic complexes Ru–Pd, Rh–Pd, and Ir–Pd, respectively. Complexes were all characterized by spectroscopic method, and some are further confirmed by X-ray crystallography. Complex Ru–Pd exhibits catalytic activities for the tandem reactions of Suzuki–Miyaura coupling/transfer hydrogenation of p-bromoacetophenone with phenylboronic acid in isopropanol, whereas Ir–Pd shows a moderate activity. However, complex Rh–Pd does not behave the same way. Furthermore, catalytic activity of these heterobimetallic complexes toward debromination/transfer hydrogenation of p-bromoacetophenonewas also investigated. The catalytic pathways of these processes were studied and discussed. This study reveals the base used in the reactions plays an important role in the reaction pathway.
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