Ligand substitution reactions of pentacyanoferrate(II) complexes with N-heterocyclic cations in aqueous solution

Abstract

Kinetic and spectroscopic studies have been carried out in aqueous solution on the formation (from Fe(CN)5OH23−) and dissociation of pentacyanoferrate(II) complexes containing 1-(4-pyridyl)pyridinium and the neutral, protonated, and N-methylated forms of 4,4′-bipyridine (BPY), 1,2-bis(4-pyridyl)ethane (BPA), and trans-1,2-bis(4-pyridyl)ethylene (BPE). The pH dependences of the formation kinetics have been analyzed in terms of the specific rate and acid dissociation constants for these ligands. The rate constants (25.0 °C, I = 0.10 M) for the formation of the dinuclear complexes (NC)5FeLFe(CN)56− have been determined for BPY (50 M−1 s−1), BPA (66 M−1 s−1), BPE (95 M−1 s−1), and pyrazine (10 M−1 s−1), and are compared with the respective rate constants for the formation of (NC)5FeLCo(NH3)5. The relationships between the formation rate constants and the size of the ligand, the number of donor sites, and the magnitude and position of charges on the ligand are discussed in terms of an ion-pair dissociative mechanism. Keywords: pentacyanoferrate(II) complexes, N-heterocycles, ligand substitution, kinetics.