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Fe(II) Mononuclear Complexes With a New Aminopyridyl Ligand Bearing a Pivaloylamido Arm. Preparation and Spectroscopic Characterizations of a Fe(III)-hydroperoxo Complex With Oxygen and Nitrogen Donors

Fe(II) Mononuclear Complexes With a New Aminopyridyl Ligand Bearing a Pivaloylamido Arm. Preparation and Spectroscopic Characterizations of a Fe(III)-hydroperoxo Complex With Oxygen and Nitrogen Donors

Marlène Martinho, Frédéric Banse, Joëlle Sainton, Christian Philouze, Régis Guillot, Guillaume Blain, Pierre Dorlet, Sophie Lecomte, Jean-Jacques Girerd

Inorg Chem. 2007 Mar 5;46(5):1709-17.

PMID: 17286400

Abstract:

Two new mononuclear FeII complexes, [(L52aH)FeII](PF6)2 (1-(PF6)2) and [(L52a)FeII]BPh4 (2-(BPh4)) have been synthesized with the new aminopyridyl ligand bearing a pivaloylamido arm L52aH (2,2-dimethyl-N-[6-({[2-(methyl-pyridin-2-ylmethyl-amino)-ethyl]-pyridin-2-ylmethyl-amino}-methyl)-pyridin-2-yl]-propionamide), or its deprotonated form L52a-. The structures of the ferrous complexes have been determined by X-ray analysis. The mononuclear FeII is in a pseudo-octahedral environment in both complexes, the six positions around the metal center being occupied by five nitrogen atoms and one oxygen atom from the ligand. Whatever the protonation state of the amide function, the structures are very similar, the FeII being 6-fold coordinated by the two amines, three pyridines, and the oxygen atom from the ligand. These two complexes exhibit an acid/base equilibrium in solution that has been studied by UV-vis spectroscopy and cyclic voltammetry in acetonitrile. The reactivity of 1-(PF6)2 with H2O2 in methanol affords the formation of a new low-spin FeIII(OOH) intermediate in which the oxygen atom is retained in the coordination sphere of the metal.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP470463435	2,2-Dimethyl-N-(5-trimethylsilanylethynyl-pyridin-2-yl)-propionamide		470463-43-5	Price

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