Solvent Exchange and Replacement

Substitution of water by oxalate in [Ru(OH2)6] involves C204H attack by a dissociative exchange mechanism as the predominant pathway/ Kinetic parameters (k, AH, AS ) for 1,10-phenanthroline substitution at cw-[Ru(bipy)2(OH2)2] , determined over the temperature range 35 to 50 °C, the pH range 3.65 to 5.5, and the solvent composition range 0 to 30% ethanol, are also claimed to be consistent with dissociative activation.  

Displacement of ethanol from [Ru(f/ -C5H5)(phen)(EtOH)] by dppm, (59), occurs rapidly even at 0°C in methanol. However, the -dppm product of this first stage is extremely reluctant to react with a second molecule of the starting complex to give the ju-dppm binuclear [ Ru(/ -C5H5)(phen) 2 (dppm)] cation.  

The synthesis and characterization of K3[Ru(CN)5(dmso)] have been reported. Kinetics of formation of, and substitution in, this pentacyano-ruthenate(II) anion are all consistent with dissociative interchange. Some longstanding uncertainties in relation to the solution chemistry of hexacyanoruthenates have been resolved. The ruthenium(II) complex can be oxidized by air in dimethylformamide solution (but not in aqueous media) to [Ru (CN)g] the latter decomposes back to ruthenium(II) in water, even when this has been fully purged with nitrogen.  

or Cl , deposited in a conducting film generated by copolymerization of the ruthenium complex with e.g., pyrrole or 3-methylthiophen, when this film is immersed in acetonitrile. Displacement of chloride is slower when the appropriate film is immersed in water this aquation process is photo-catalyzed. Variable-temperature NMR has given some information on intramolecular conformational changes in the constrained ligands (62) and (63) [X=—CHj— to — (CH2)4—]. The inversion barrier of 44kJmol  

8 Inert-Metal Complexes Other Inert Centers 

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