The Affinity of Indium(III) for Nitrogen-donor Ligands in Aqueous Solution. A Study of the Complexing of Indium(III) with Polyamines by Differential Pulse Voltammetry, Density Functional Theory, and Crystallography

The affinity of In(III) for N-donor ligands was investigated by differential pulse voltammetry, DFT calculations, and crystallography. The structure of [In(tpen)(CH3COO)](ClO4)2 ・ 0.5H2O (1) is reported (tpen = N,N,N´ ,N´-tetrakis(2-pyridylmethyl)ethylenediamine): Monoclinic, P21/n, a = 8.687(4), b = 7.767(8), c = 20.432(10) Å , β = 93.372(8)°, Z = 4, R = 0.0518. The In(III) center is 7-coordinate, with six In-N bonds to the tpen ligand in the range 2.306 - 2.410 Å, and a unidentate acetate group with In-O = 2.247 Å. The formation constants of In3+ in 0.1 M NaNO3+ at 25 °C are (M = In(III), L = ligand, H = proton): L = triethylenetetramine, logβ (MLH2) = 25.3±}0.3, logK1 = 14.43±}0.09, and logβ (ML(OH)2) = 27.7±}0.1; tetraethylenepentamine, logβ (MLH) = 20.8±}0.2, and ML (logβ (ML) = 20.1±}0.3); diglycolic acid, (logβ (MLH) = 8.06±}0.06), logK1 = 6.02±} 0.06, logβ2 = 9.40±}0.08; tpen, logK1 = 17.71±}0.07; N,N´-bis(2-pyridylmethyl)ethylenediamine, logK1 = 14.69±}0.05; 1,10-phenanthroline, logK1 = 6.81±}0.07, logK2 = 6.44±}0.07, logK3 = 6.20±}0.08. Correlations are shown between the determined formation constants for the polyamines and logK1(NH3) values for a wide variety of metal ions. For M(II) ions, the log K1(NH3) values are experimental data, but for M(III) ions the data are predicted by an empirical dual-basicity equation, including logK1(NH3) = 4.0 for In(III). DFT calculations are used to obtain ΔE for the reaction [M(H2O)6]n+ + NH3 ⇆[M(H2O)5NH3]n+ + H2O for M(II) through M(IV) ions in water, represented as a structureless medium with the dielectric constant of water. Correlations are found that support the predicted value of logK1(NH3) for In(III) of 4.0. The nature of the intercepts on such correlations are discussed.