CHEMISTRY OF POLYFUNCTIONAL MOLECULES .12 1. CYCLOPENTADIENYLRUTHENIUM(II) COMPLEXES OF BIS(DIPHENYLPHOSPHANYL)AMINE AND BIS(DIPHENYLPHOSPHANYL)AMIDE, AND OF N,N-BIS(DIPHENYLPHOSPHANYL)METHYLAMINE AND N,N-BIS(DIPHENYLPHOSPHANYL)ETHYLAMINE

This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C6H5)(2)P](2)NR (R = H:Hdppa, 1a; R = CH3: dppma, 1b; R = C2 H5: dppea, 1c; R = Li:Lidppa, 1d). Treatment of 1a, d with CpRuCl(PPh( 3))(2) (Cp = eta(5)-C5H5, Ph = C6H5, 2) in a molar ratio of 1:1 in boi ling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh(3) (6). The ionic complexes [CpRu(Ph(2)P-NR-PPh (2))PPh(3))Cl (R = CH3: 4a; R = C2H5: 4b) are formed by the reaction o f 1b, c with 2. One pot reactions of 1a-c with 2 in the presence of NH 4PF6 in boiling CH3OH give only the ionic compounds CCpRu(Ph(2)P-NR-PP h(2))(PPh(3))]PF6 (R = H, CH3, C2H5; 5a-c). The sulfur dioxide and hyd ride complexes [CpRu(Hdppa)eta(1)-SO2]Cl (7) and CpRu(H)Hdppa (8) are obtained by the interaction of 3 with SO2 or NaOCH3. All compounds are characterized as far as possible by IR, Raman, P-31{H-1} NMR, H-1 NMR , C-13{H-1} NMR, FD mass spectra, and their conductivity in CH2Cl2 sol ution. The X-ray crystal structures of 3 and 5a reveal that the P(1)-N (1)-P(2) angle of the coordinated ligand la in both complexes is reduc ed to about 100 degrees in comparison to free uncoordinated 1a (119 de grees). This small angle leads to a short P(1)-P(2) bond distance of 2 59.4 pm in 3 and 254.3 pm in 5a. The molecules of 3 are connected by i ntermolecular (NH ... Cl) hydrogen bridging bonds forming chains along the z axis of the unit cell. The crystals of 5a contain two independe nt pairs of ions in the unit cell (Z = 8). In 5a no hydrogen bonds exi st between the NH-groups and the PF6- anions.