Outer-sphere and inner-sphere ligand protonation in metal complexation kinetics: the lability of EDTA complexes

A generic framework, based on the Eigen mechanism, is formulated to describe the formation/dissociation kinetics of inner-sphere metal complexes that may undergo protonation. In principle, all protonated forms of the ligand contribute to the formation of the precursor outer-sphere complexes, but only the sufficiently stable ones effectively contribute to the overall rate of inner-sphere complex formation. The concepts are illustrated by experimental data for Cd(II)-EDTA complexes. Up to pH 8 the dissociation flux in this system is dominated by the protonated inner-sphere complex, even though it is a very minor component of the equilibrium speciation in bulk solution. The results highlight the importance of distinguishing between the thermodynamically predominant species versus the kinetically relevant ones in considerations of dynamic speciation analysis and bioavailability in natural and engineered systems.