The kinetics of mercury(II)-catalyzed substitution of cyanide ligand in hexacyanoruthenate(II) by pyrazine (Pz) has been investigated spectrophotometrically at 370 nm in aqueous medium. The reaction exhibits firstorder dependence on [Pz] at low concentrations, then reaches a maximum value, and finally decreases at high [Pz]. The reaction has a variable-order dependence in [Ru(CN) 64-], unity at lower [Ru(CN) 6 4-], and fractional order, not tending to zero order at higher [Ru(CN) 64-]. The effects of pH, ionic strength, concentration of catalyst, and temperature variations have been studied. The activation parameters for the reaction were calculated. We propose a solvent assisted interchange dissociative (I d ) mechanism for the reaction.
The kinetics and mechanism of substitution reaction of [Ru(CN) 5 H 2 O] 3− anion with two naphthalene-substituted ligands viz. L n = nitroso-R-salt (NRS) and α-nitroso-β-naphthol (αNβN) have been studied spectrophotometrically by monitoring an increase in absorbance at λ max = 525 nm corresponding to metal to ligand charge transfer (MLCT) transitions due to formation of substituted [Ru(CN)
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