Studies on the kinetics and mechanism of dissociation of copper(II) and nickel(II) complexes of the macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene in perchloric acid media |
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Authors: | Ashis Kumar Pondit Asim Kumar Das Soma Gangopadhyay Debabrata Banerjea |
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Institution: | (1) Inorganic Chemistry Division, Department of Chemistry, University College of Science, 92 A.P.C. Road, 700009 Calcutta, India |
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Abstract: | Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML2+ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (kobs) showing acid dependence; for the nickel(II) complex (kobs)=kO+kHH+], the ko path is however absent with the copper(II) complex. At 60°C (I=0.1M) the kH values areca 10–4 M–1 s–1 for both complexes; k
H
Cu
/k
H
Ni
=ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values copper(II) complex, 29.4±0.5 kJ mol–1; nickel(II) complex, 35.6±1.5 kJ mol–1] with highly negative S values for copper(II), –215.5 ±6.1 JK–1 mol–1 and for nickel(II), –208.1 ±5.6 JK–1 mol–1] which are much higher than the entropy of solvation of Ni2+ (ca. –160 JK–1 mol–1) and Cu2+ (ca. –99 JK–1 mol–1) ions; significant solvation of the released metal ions and the ligand is indicated. |
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