New neutral and cationic η6-arene ruthenium complexes with phosphine and amine ligands: Syntheses and molecular structures of [(η6-p-cymene)Ru(NH(2)CH(2)C(6)H (5))Cl2], [(η6-C6Me 6)Ru(PPh2Py)Cl2] and [(η6-C 6Me6)Ru(PPh2Py)Cl]+

Article abstract of DOI:10.1016/j.poly.2004.09.031

The dimeric complex [(η⁶-C₆Me₆) Ru(μ-Cl)Cl]₂ reacts with diphenyl-2-pyridyl-phosphine to yield a neutral P-coordinated ruthenium(II) complex [(η⁶-C ₆Me₆)Ru(PPh₂Py)Cl₂] as well as a cationic P,N-chelating complex [(η⁶-C₆Me ₆)Ru(PPh₂Py)Cl]⁺. The monomeric complex [(η⁶-p-cymene)Ru(PPh₃)Cl₂] can react with amine ligands to yield chiral complexes. Representative complexes have been characterized by single-crystal X-ray study. The complex [{(η⁶-p- cymene)Ru(μ-Cl)Cl}₂] (1) reacts with benzylamine to give a neutral N-coordinated complex of the type [(η⁶-p-cymene)Ru(NH ₂CH₂C₆H₅)Cl₂] (2). The complex [(η⁶-p-cymene)Ru(PPh₃)Cl₂] (3) reacts with amine ligands to yield chiral complexes [(η⁶-p- cymene)Ru(PPh₃)(NH₂-R)Cl]⁺ [R = CH ₂C₆H₅ (4a), p-ClC₆H₄ (4b), p-NO₂C₆H₄ (4c)]. Complexes 1 and 3 react with N,N-donor chelating 1,2-phenylenediamine (PDA) giving cationic complexes 5 and 6, respectively. The complex [(η⁶-C₆Me ₆)Ru(μ-Cl)Cl]₂ (7) reacts with diphenyl-2- pyridylphosphine to yield a neutral P-coordinated ruthenium(II) complex [(η⁶-C₆Me₆)Ru(PPh₂Py)Cl ₂] (8) as well as a cationic P,N-chelating complex [(η⁶-C₆Me₆)Ru(PPh₂Py)Cl] ⁺ (9). The complex 9 undergoes substitution reactions with acetonitrile and 1,1-diphenyl-2-propyn-1-ol ligands. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data. The molecular structures of the representative complexes [(η⁶-p- cymene)Ru(NH₂CH₂C₆H₅)Cl ₂] (2), [(η⁶-C₆Me₆)Ru(PPh ₂Py)Cl₂] (8) and [(η⁶-C₆Me ₆)Ru(PPh₂Py)Cl]BF₄ (9) were established by single-crystal X-ray diffraction studies.