✦ LIBER ✦

Re-examination of the formation of dinitrosyl–iron complexes during reaction of S-nitrosothiols with Fe(II)

✍ Scribed by Simona Costanzo; Stephane Ménage; Roberto Purrello; Raffaele P Bonomo*; Marc Fontecave*

Publisher: Elsevier Science
Year: 2001
Tongue: English
Weight: 136 KB
Volume: 318
Category: Article
ISSN: 0020-1693
DOI: 10.1016/s0020-1693(01)00402-9

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✦ Synopsis

The reaction of S-nitrosothiol compounds with ferrous ions in solution has been investigated and the generated dinitrosyl-iron complexes have been characterized. During the reaction of S-nitrosocysteamine with Fe(II) in water solution in the presence of a twofold excess (with respect to iron) of cysteamine hydrochloride (CSH), an EPR-silent dinuclear iron complex (complex A of formula [Fe 2 (RS) 2 (NO) 4 ]) was formed as the major species and was characterized by FAB MS + , UV-Vis, NMR and IR spectroscopies. In the presence of a large excess of CSH (CSH/Fe(II)=20:1), a green paramagnetic mononuclear complex (complex B of formula [Fe(RS) 2 (NO) 2 ] -) was formed. From EPR and UV-Vis data, and also on the basis of the few crystallographic structures known for similar complexes, complex B is proposed to display a distorted tetrahedral geometry (C 26 ), approaching a trigonal bipyramid with a missing ligand, with the unpaired electron mainly localized on the d z 2 orbital of the iron characterized by a d 9 electronic configuration.

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