Fe(II) and Fe(III) mononuclear complexes with a pentadentate ligand built on the 1,3-diaminopropane unit. Structures and spectroscopic and electrochemical properties. Reaction with H2O2.

Abstract

Two new iron complexes, [L(5)(3)Fe(II)Cl]PF(6) (1.PF(6)) and [(L(5)(3)H(+))Fe(III)Cl(3)]PF(6) (2.PF(6)), were synthesized (L(5)(3) = N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine), and their molecular structures were determined by X-ray crystallography. Their behavior in solution was studied by UV-vis spectroscopy and electrochemistry. Upon addition of a base to an acetonitrile solution of 2, the new unsymmetrical dinuclear complex [L(5)(3)Fe(III)OFe(III)Cl(3)](+) was detected. Treating 1 with hydrogen peroxide has allowed us to detect the low spin [L(5)(3)Fe(III)OOH](2+). Its spectroscopic properties (UV-vis, EPR and resonance Raman) are similar to those reported for related FeOOH complexes obtained with amine/pyridine ligands. Using stopped-flow absorption spectroscopy, the formation and degradation of [L(5)(3)Fe(III)OOH](2+) has been monitored, and a mechanism is proposed to reproduce the kinetic data.