Anomalous magnetism of iron(II) complexes of methyl-substituted pyridylthiazoles

Abstract

Bis-ligand iron(11) and nickel(11) complexes of the potentially tridentate chelating agents 2-(3-methyl-2-pyridylamino)-4-(2-pyridyl)thiazole and 2-(4-methyl- 2-pyridylamino)-4-(2-pyridyl)thiazole are described. The electronic spectra of the nickel(11) complexes show that the field strengths of the ligands are in the neighbourhood of the Crossover region for iron(11). The magnetic properties of the cationic iron(11) complexes are anomalous and consistent with a spin-equilibrium involving the nearly equi-energetic ⁵T₂ and ¹A₁ states of the metal atom. The magnetism shows a strong dependence on the associated anion. 2-(6-Methyl-2-pyridylamino)-4- (2-pyridyl)thiazole is also described. In its bis-ligand iron(11) complexes it functions as a bidentate chelating agent and the complexes are high-spin. All three ligands may be deprotonated to yield inner complexes with iron(11) which in some instances have anomalous magnetic properties associated with the presence of a spin-equilibrium. 2-(6-Methyl-2-pyridyl)-4-(2-pyridyl)thiaole and its bis-ligand iron(11) and nickel(11) complexes are also described. The iron(11) complexes are high-spin and show normal temperature dependence of their magnetism.