Issue 22, 1977

Equilibria and kinetics of complex formation between zinc(II), lead(II), and cadmium(II), and 12-, 13-, 14-, and 15-membered macrocyclic tetra-amines

Abstract

Polarographic methods have been used to determine the equilibria and kinetics of reaction of ZnII, PbII, and CdII with 12- to 15-membered macrocyclic tetra-amines including 1,4,7,10-tetra-azacyclododecane (L1), 1,4,7,10-tetra-azacyclotridecane (L2), 1,4,8,11-tetra-azacyclotetradecane (L3), and 1,4,8,12-tetra-azacyciopentadecane (L4) in acetate buffer solutions. Unlike the copper(II) system. the stability constants of the zinc complexes hardly change with macrocyclic ring size : log KZnL= 16.2, 15.6, 15.5, and 15.0 for L1, L2, L3, and L4, respectively (I0.20 mol dm–3 and 25 °C). The much larger CdII and PbII form complexes only with L1: log KCdL 14.3 and log KPbL, 15.9. The 103–105 times greater stabilities of the macrocyclic complexes compared with the related complexes of linear terra-amines are all due to favourable entropy changes, regardless of the metal-ion size. The rate law for complex formation in acetate buffers is d[ML]/dt=kH[M(O2CMe)+][HL+]+k2H[M(O2CMe)+][H2L2+] for all the metal ions. A comparison with reactions of CuII and L1–L4 shows that the values of kH parallel the well established rates of water exchange of the aquametal ions.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1977, 2269-2276

Equilibria and kinetics of complex formation between zinc(II), lead(II), and cadmium(II), and 12-, 13-, 14-, and 15-membered macrocyclic tetra-amines

M. Kodama and E. Kimura, J. Chem. Soc., Dalton Trans., 1977, 2269 DOI: 10.1039/DT9770002269

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