Kinetics and Mechanism of the Ligand Substitution Reaction of the Mercury(II)-4-(2-pyridylazo)resorcinol Complex with 1,2-Cyclohexanediamine-N,N,N′,N′-tetraacetic Acid

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Kinetics and mechanism of the ligand substitution reaction of the mercury(II)-PAR complex with CyDTA were studied at 25°C in the presence of halogenide ion at an ionic strength of 0.1. The rate law can be written as −\fracd[Hg(par)22−]dt=(k1′[H+]+k2′+k3,X′[H+][X−])\frac[Hg(par)22−][Hpar−][Hcydta3−] where X− refers to a halogenide ion (chloride, bromide, iodide). The rate constants k1′, k2′, and k3,X′ were determined as: k1′=(2.4±0.1)×107 M−1 sec−1, k2′=(1.9±0.1)×10−2 sec−1, k3,Cl′=(4.5±0.2)×109 M−2 sec−1, k3,Br′=(3.2±0.1)×1011 M−2 sec−1, k3,I′=(5.6±0.2)×1014 M−2 sec−1. The rate constants for the paths involving mixed hydroxo and halogeno complexes (k2′ and k3,X′) are quantitatively accounted for in terms of electron donation of ligands OH− and X−.
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