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The reaction between Pd(N,N')Cl 2  [(N,N'= l-methyl-2-(arylazo)imidazole (RaaiMe), p-RC 6 H 4 - N=N-C 3 H 2 NN-1 -Me; 2-(arylazo)pyridine (Raap), p-C 6 H 4 -N=N-C 5 H 4 N; 2- (arylazo)pyrimidine (Raapm), p-C 6 H 4 -N=N-C 4 H 3 N 2 ; where R=H (a), Me (b), CI (c)] and apicolinic acid (α-picH) have been examined spectrophotometrically in MeCN solution at 298K. The product is Pd(a-pic) 2  which has been supported by pure compound synthesis from Na2[PdCl4] and α-picH. The kinetics of the nucleophilic substitution reaction has been studied under pseudo-first-order condition. The reaction proceeds in a biphasic manner. The kinetic analysis confirms the nucleophilic association path. External addition of CI -  (LiCl) suppresses the rate. On considering the consecutive reaction A-&gt; B-&gt; C the rate data have been evaluated. Each phase shows first-order dependence on [α-picH]. Rate-1 = {a 1 +k 1 [(α-picH]}[ Pd(N,N')Cl 2 ]; rate-2 = {a 1 +k 2 [(α-picH]}[Pd(N,N')Cl 2 ], with the k 1  (first phase rate constant) &gt; k 2  (second phase rate constant). Increase in π-acidity of the ligand N,N' increases the rate and follows the order: Pd(RaaiMe)Cl 2  &lt; Pd(Raap)Cl 2  &lt; Pd(Raapm)Cl 2  .

Kinetics and mechanism of reaction of α-picolinic acid with dichloro-{2-(arylazo)- heterocycle}palladium(II) complexes