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Spin-Transition Behaviour of Transition Metal Complexes with 2,6-bis-(Benzimidazol-2′-yl)-pyridine Induced by Deprotonation of the Complex
2,6-bis-(Benzimidazol-2′-yl)-pyridine (bzimpy = H2L) acts as a bidentate ligand when combining with transition metal ions.The complexes (ClO4)2 (M = Fe(2+), Mn(2+), Zn(2+), Co(2+), and Ni(2+)) were obtained as solids.The protonation constants (log K) for the ligand and the complexes were evaluated in 30:70 (v/v) H2O:EtOH at 293 K and at constant ionic strength of 0.12M KCl.Coordination of the ligand to the metal ions leads to an increase of acidity of the imino-hydrogen of the benzimidazole group of the ligand as a function of the complex stability.Deprotonation leads to a spin-state transition (intermediate spin-state –> low-spin) of the iron(II)-complex, followed by a shift of the metal-to-ligand charge transfer band (MLCT) to lower energies (lambdamax = 563 to 580 nm).The d-d absorption bands are found to shift to higher energies and the low-spin isomer is favoured at room temperature.An opposite shift of the MLCT band (lambdamax = 563 to 557 nm) is observed when HClO4 is added to the complex solution, rendering the high-spin state of the complex more favourable. – Keywords. 2,6-bis-(Benzimidazol-2′-yl)-pyridine; Spin-Crossover behaviour; Deprotonation; Transition metal complexes.
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Reference£º
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method