Structure and properties of μ2-S-[bis(benzenethiolato)tetranitrosyldiiron] in solution

Abstract

Dinuclear iron tetranitrosyl complex with the composition [Fe 2 (SPh) 2 (NO) 4 ] (1) was syn thesized and its single crystals and polycrystals were studied by X ray diffraction, IR spectro scopy, and elemental analysis. The decomposition products of complex 1 were investigated by electrochemical method and mass spectrometry. The mass spectrum of a solution of complex 1 shows two groups of ions: the primary decomposition products of 1 in solution (the complex ions [Fe(SPh)(NO) 2 (NO 2 )] -, [Fe(SPh) 2 (NO)] -, and [Fe(SPh) 2 (NO) 2 ] -) and a series of the ions [FeO 2 + n(NO)]and [FeO 3 + n(NO)] -(n = 0-4), which are formed in secondary reactions. The structures of the complexes, which were formed through the Fe-NO bond dissociation and the replacement of the NO ligand by aqua and oxygen ligands in complex 1, and the structure of the complex [FeO 3 ]were studied by quantum chemical modeling.

Influence of aromatic ligand on the redox activity of neutral binuclear tetranitrosyl iron complexes [Fe2(μ-SR)2(NO)4]: experiments and quantum-chemical modeling

“…Analysis according to Bader produces a charge close to 1 on the iron atom, this being consistent with a common electronic structure of iron-sulfur nitrosyl complexes. 27 For complexes 4 and 5, both methods suggest that upon transition from the neutral molecule to the monoanion the charge on the iron atom becomes more positive, while the NO group becomes more negative. Consequently, the Fe-N bond in the anion of these complexes is more polar than in the neutral molecule, and therefore the anion is expected to be a better NO donor than the neutral complex.…”