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PROTONATION CONSTANTS AND SOLVENT DEPENDENT SPIN-CROSSOVER BEHAVIOUR OF IRON(II)-2-(2′-PYRIDYL)BENZIMIDAZOLE COMPLEXES
Abstract:Abstract

2-(2′-Pyridyl)benzimidazole (pybzim = LH) coordinates to iron(II) as a bidentate and forms the tris-ligated complex, Fe(pybzim)3]2+ as isolated in the solid. Titration of Fe(pybzim)3]2+ with base demonstrates the successive deprotonation of the imino hydrogens of the coordinated ligands. Protonation constants for the free ligand, pybzim (Iog10 K H = 11.33) and the complex, Fe(pybzim)3]2+ (log10 K H 1 = 9.58, log10 K H 2 = 8.13 and log10 K H 3 = 6.97) were measured in 30% (v/v) H2O/EtOH. Results show that coordination to iron(II) increases the acidity of the imino hydrogen of the ligand. Spin-crossover behaviour of the complex were studied in different solvents ME, AC, AN, NM, NB, DMF, DMSO and ANL. The complex shows strong spin-crossover behaviour which is solvent dependent. Values of the spin-equilibrium constant (K sc) and the associated thermodynamic parameters (ΔH sc = 18.1–21.3 kJ mol?1 and δS sc = 69.6–84.4JK?1 mol?1) were calculated. An increase of the enthalpy is observed with increasing donor number (DN) of the solvent.
Keywords:2-(2′-Pyridyl)benzimidazole (pybzim)  [Fe(pybzim)3]2+  protonation constants  spin-crossover  non-aqueous solvents  donor number
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