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A dinitrosyliron complex within the homoleptic Fe(NO)4 anion: NO as nitroxyl and nitrosyl ligands within a single
Zong-Sian Lin1, Tzung-Wen Chiou, Kuan-Yu Liu
1Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Abstract:
Nitrosylation of the chelate-thiolate-containing dinitrosyliron complex (DNIC) [(S(CH(2))(3)S)Fe(NO)(2)](-) triggers nitric oxide (NO) activation to generate the homoleptic nitrosyl {Fe(NO)(2)}(9) DNIC [Fe(NO)(4)](-) (1) made up of two nitroxyls (or two NO anions) attached to a delocalized {Fe(NO)(2)}(9) motif. The significantly longer N3-O3/N4-O4 [1.380(12) and 1.280(12) Å] and Fe1-N3/Fe1-N4 [2.008(11) and 2.045(10) Ǻ] bond distances reflect that N3-O3 and N4-O4 of complex 1 may act as the nitroxyl-coordinated ligands. That is, the electronic structure of the DNIC 1 is best described as a {Fe(NO)(2)}(9) motif coordinated by two nitroxyl (NO(-)) ligands.