ISSN:
1434-4475
Keywords:
Cyclopentadienylruthenium(II) complexes
;
Diphosphazane ligands
;
Crystal structures
;
IR
;
Raman
;
NMR
;
UV/VIS
;
Mass spectra
;
Hydrogen bridging bonds
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C6H5)2P]2NR (R=H:Hdppa,1a;R=CH3:dppma,1b;R=C2H5:dppea,1c;R=Li:Lidppa,1d). Treatment of1a, d with CpRuCl(PPh3)2 (Cp=η5-C5H5, Ph=C6H5,2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh3 (6). The ionic complexes [CpRu(Ph2P-NR-(PPh2)PPh3)Cl (R=CH3:4a;R=C2H5:4b) are formed by the reaction of1b,c with2. One pot reactions of1a–c with2 in the presence of NH4PF6 in boiling CH3OH give only the ionic compounds [CpRu(Ph2P-NR-PPh2)(PPh3)]PF6 (R=H, CH3, C2H5;5a–c). The sulfur dioxide and hydride complexes [CpRu(Hdppa)η1-SO2]Cl (7) and CpRu(H)Hdppa (8) are obtained by the interaction of3 with SO2 or NaOCH3. All compounds are characterized as far as possible by IR, Raman,31P{1H} NMR,1H NMR,13C{1H} NMR, FD mass spectra, and their conductivity in CH2Cl2 solution. The X-ray crystal structures of3 and5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand1a in both complexes is reduced to about 100° in comparison to free uncoordinated1a (119°). This small angle leads to a short P(1)–P(2) bond distance of 259.4 pm in3 and 254.3 pm in5a. The molecules of3 are connected by intermolecular (NH...Cl) hydrogen bridging bonds forming chains along thez axis of the unit cell. The crystals of5a contain two independent pairs of ions in the unit cell (Z=8). In5a no hydrogen bonds exist between the NH-groups and the PF 6 − anions.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00807018
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