Ligand Steric Interactions Modulate Multidentate Ligand Exchange Pathways: Kinetics of Nickel(II) Ion Capture from...

Exchange reactions between multidentate ligands (also known as chelating agents) contribute to kinetic control of metal ion speciation in aquatic environments. However, the complexity of the stepwise reaction mechanism complicates predictions of kinetic behavior (rates, rate laws, and mechanisms). Clarity is achieved with the adjunctive-semijunctive-disjunctive paradigm, which categorizes multidentate ligand exchange pathways along a continuum according to the decreasing ease of forming intermediate mixed-ligand ternary complexes. In order to better understand how steric interaction between entering and leaving ligands affects reaction pathways and kinetic behavior, we use a capillary electrophoresis method to monitor exchange between trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetate (CDTA) and nickel(II) complexes with each of the following N-substituted iminodiacetate ligands (XIDA), iminodiacetate (IDA), methyliminodiacetate (MIDA), and benzyliminodiacetate (BIDA). Kinetic modeling indicates that reactions between CDTA and 1:1 nickel-XIDA complexes occur via parallel adjunctive and disjunctive pathways. With greater steric bulk of N-substituents on iminodiacetate, product formation via a disjunctive pathway increases while formation via the adjunctive pathway decreases. Kinetic analysis demonstrates how the shift in reaction pathways has a nonlinear effect on both the magnitude of the overall rate and the rate dependence on ligand concentrations. Furthermore, we discuss the implications of this work for understanding dynamic metal ion speciation in the environment.