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New Members of the {Fe(NO)2}10 Dinitrosyliron Complexes Bound with [Thiolate, Thiolate] and [Amide, Amide] Ligations

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journal contribution
posted on 06.09.2010, 00:00 by Jheng-Hong Wang, Chien-Hong Chen
The first dianionic {Fe(NO)2}10 dinitrosyliron complexes (DNICs) [Fe(SC7H4SN)2(NO)2]2− (1) and [Fe(OC7H4SN)2(NO)2]2− (2), coordinated with thiolates and amides, were prepared by the reaction of Fe(TMEDA)(NO)2 with 2 equiv of ligands [SC7H4SN] and [OC7H4SN], respectively. The reversible interconversion between the dianionic {Fe(NO)2}10 DNICs 1/2 and the anionic {Fe(NO)2}9[Fe(SC7H4SN)2(NO)2] (3)/[Fe(OC7H4SN)2(NO)2] (4), respectively, was demonstrated. The transformation of DNICs 2 and 3 into the thermally stable DNICs 1 and 4, respectively, via the ligand-exchange reaction reveals that [OC7H4SN] shows a high binding affinity toward the {Fe(NO)2}9 motif and [SC7H4SN] prefers the {Fe(NO)2}10 motif. This result rationalizes that the intermolecular electron transfer from DNIC 2 to DNIC 3 occurs to lead to the formation of the more thermally stable DNICs 1 and 4 upon the reaction of DNICs 2 and 3 in tetrahydrofuran.