Dynamics of the Bis-Tris and High Spin-Low Spin Equilibria of 2-(2′-Pyridyl)imidazoleiron(II) Complexes in Dimethyl Sulfoxide Solutions

Abstract

Ultrasonic and temperature-jump relaxation kinetics have been used to observe, respectively, the spin equilibrium and tris-bis ligand dissociation equilibrium of the 2-(2′-pyridyl) imidazoleiron (II) complexes in dimethyl sulfoxide solutions.

In the ultrasonic experiments a single relaxation curve describes the excess sound absorption with a relaxation time of 73±3 ns. This was identified as perturbation of the singlet-quintet spin equilibrium by comparison with previous laser temperature-jump measurements in other solvents and by the temperature dependence of the relaxation amplitude. The equilibrium constant for the singlet-quintet transition was determined by the Evans n.m.r . method to be 0.48 at 298 K. From the relaxation time and the equilibrium constant the rate constants for the spin-equilibrium transition can be calculated to be k₁₅ of 4.5×10⁶ s^-1 and k₅₁ of 9.4×10⁶s^-1. In the temperature-jump experiments a millisecond relaxation time was observed. The dependence of the relaxation time on the concentration of the free ligand is of the form k_obs = a + b[L]. From the ratio b/a an equilibrium constant for the perturbed process can be calculated. An independent measure of this equilibrium constant was obtained from spectrophotometric measurements. The rate constants for the formation and dissociation of the tris complex are calculated to be 2.8 × 10⁴ dm³ mol^-1 s^-1 and 2.1 × 10² s^-1, respectively, at 298 K.