Abstract
The isoelectronic complexes [(η6-C6H6)Ru(Ph)2PPyCl2] (1) and [(η5Me5)Rh(Ph5PPy)Cl2] (3) in which 2-(diphenylphosphino)pyridine (Ph2PPy) is P-monodentate, have been obtained by treating the complexes [{(η6-C6H6)RuCl2}2], and [{(η5-C5Me5)RhCl2}2], respectively, with Ph2PPy in the molar ratio 1:1, Coordination of the pyridine nitrogen atom to metal in1 and3 has been achieved by removing one chloride with AgPF6. By this route the cationic complexes [(η6-C6H6)Ru(Ph2PPy)Cl]PF6 (2) and [(η5-C5Me5)Rh(Ph2PPy)Cl]PF6 (4) in which the Ph2PPy is chelating, have been obtained. The reaction of [(η6-C6Me6Ru(Ph2PPy)Cl2] (1) with cis-[Pt(DMSO)2Cl2] in CH2Cl2 gives the ionic binuclear complex [(η6-C6Me6)Ru(Ph2PPy)(μ-Cl)Pt(DMSO)Cl2]Cl (5a) which was also obtained as the [PF6]− salt,5b. 1H and 31P{1H} NMR spectra support structures for5a and5b with the Ph2PPy chelated to ruthenium(II) and a chloride bridging to platinum(II). The DMSO is S-bonded and the geometry at platinum(II) is cis. Upon attempted reaction of1 with cis-[Pd(tBuNC)2Cl2] in CH2Cl2 at room temperature, the reagents were recovered unchanged after 7 h. The reactions of [(η5-C5Me5)Rh(Ph2PPy)Cl2] (3) with cis-[Pd(tBuNC)2Cl2] and cis-[Pt(DMSO)2Cl2] afford the known cis-[Pd(tBuNC)(Ph2PPy)Cl2] and cis-[Pt(DMSO)(Ph2PPy)Cl2], together with {[(η5-C5Me5)RhCl2}2]. The reaction of [{(C8H12)RuCl2}n] with [(η5-C5H5)Rh(CO)(Ph2PPy)] in CH2Cl2 in the molar ratio 1:1, is very complex. We have separated [(C8H12)RuCl((μ-Cl(μ-Ph2PPy)Rh(η5-C5H5)] (6) by chromatography column. The bridging Ph2PPy is P-bonded to the rhodium(I). On allowing CH2Cl2 solution of6 to stand, crystals of the rhodium(III) complex [(η5-C5H5)RhCl2(Ph2PPy)] (7) are formed. Probably a very slow intramolecular redox process involving the RuIIRhI species6 is responsible of the formation of7. In the complex, the 2-(diphenylphosphino)pyridine is monodentate, coordinating through phosphorus.
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