New neutral and cationic η6-arene ruthenium complexes with phosphine and amine ligands: syntheses and molecular structures of [(η6-p-cymene)Ru(NH2CH2C6H5)Cl2], [(η6-C6Me6)Ru(PPh2Py)Cl2] and [(η6-C6Me6)Ru(PPh2Py)Cl]+

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(NH2CH2C6H5)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=CH2C6H5 (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-C6Me6)Ru(μ-Cl)Cl]2 (7) reacts with diphenyl-2-pyridylphosphine to yield a neutral P-coordinated ruthenium(II) complex [(η6-C6Me6)Ru(PPh2Py)Cl2] (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)Cl2] (2), [(η6-C6Me6)Ru(PPh2Py)Cl2] (8) and [(η6-C6Me6)Ru(PPh2Py)Cl]BF4 (9) were established by single-crystal X-ray diffraction studies.