Kinetics and mechanism of ligand substitution of mono(polyamine)-nickel(II) complexes with 4-(2-pyridylazo)resorcinol |
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| Authors: | Hari C Bajaj Surendra Prasad Radhey M Naik Prem C Nigam |
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| Institution: | (1) Division of Coordination Chemistry and Homogeneous Catalysis, Central Salt and Marine Chemicals Research Institute, 364 002 Bhavnagar, India;(2) Department of Chemistry, Indian Institute of Technology, 208 016 Kanpur, India;(3) Department of Chemistry, Manipur University, 795 003 Imphal, India |
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| Abstract: | Summary The kinetics and mechanism of ligand substitution reactions of tetraethylenepentamine nickel(II), Ni (Teren), and triethylenetetraamine nickel(II), Ni(Trien), with 4-(2-pyridylazo)resorcinol (parH2) have been studied spectrophotometrically at I=0.1 M (NaClO4) at 25°C. In both systems two distinct reaction steps are observed. The rapid first step follows the rate law dNi(Polyamine)(ParH2)]/dt=k1 Ni(Polyamine)] ParH2]. The formation of ternary complexes of Ni (Polyamine) with ParH2 has been investigated under second order equal concentration conditions. The values of second order rate constants for the Trien and Teren reactions are (2.1±0.2)×104 M–1s–1 and (7.8±0.6)×103 M–1s–1 respectively at pH=9.0, I=0.1 M and 25°C.The rate law for the second step may be written as dNi(Par)2]/dt=k2Ni(Polyamine)(ParH2)]. Values of k2 for the Trien and Teren systems are (2.5±0.1)×10–4 s–1 and (4.76±0.3)×10–5 s–1 respectively. |
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