The fluxional terminal and semibridging NO-coordinate ligands of DNIC [Fe4(μ3-S)2(μ2-NO)2(NO)6](2-), a precursor of Roussin's black salt (RBS), are characterized by IR ν(NO), (15)N (NO) NMR and single-crystal X-ray diffraction.
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Iron(III) bound by hydrosulfide anion ligands: NO-promoted stabilization of the [Fe(III)-SH] motif.
J Am Chem Soc
July 2014
Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013, Taiwan.
Spontaneous transformation of the thermally stable [HS](-)-bound {Fe(NO)2}(9) dinitrosyl iron complex (DNIC) [(HS)2Fe(NO)2](-) (1) into [(NO)2Fe(μ-S)]2(2-) (Roussin's red salt (RRS)) along with release of H2S, probed by NBD-SCN (NBD = nitrobenzofurazan), was observed when DNIC 1 was dissolved in water at ambient temperature. The reversible transformation of RRS into DNIC 1 (RRS → DNIC 1) in the presence of H2S was demonstrated. In contrast, the thermally unstable hydrosulfide-containing mononitrosyl iron complex (MNIC) [(HS)3Fe(III)(NO)](-) (3) and [Fe(III)(SH)4](-) (5) in THF/DMF spontaneously dimerized into the first structurally characterized Fe(III)-hydrosulfide complexes [(NO)(SH)Fe(μ-S)]2(2-) (4) with two {Fe(NO)}(7) motifs antiferromagnetically coupled and [(SH)2Fe(μ-S)]2(2-) (6) resulting from two Fe(III) (S = 5/2) centers antiferromagnetically coupled to yield an S = 0 ground state with thermal occupancy of higher spin states, respectively.
View Article and Find Full Text PDFThe dinitrosyliron complex [Fe₄(μ₃-S)₂(μ₂-NO)₂(NO)₆]²⁻ containing bridging nitroxyls: ¹⁵N (NO) NMR analysis of the bridging and terminal NO-coordinate ligands.
Dalton Trans
June 2014
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
The fluxional terminal and semibridging NO-coordinate ligands of DNIC [Fe4(μ3-S)2(μ2-NO)2(NO)6](2-), a precursor of Roussin's black salt (RBS), are characterized by IR ν(NO), (15)N (NO) NMR and single-crystal X-ray diffraction.
View Article and Find Full Text PDFNitrate-to-nitrite-to-nitric oxide conversion modulated by nitrate-containing {Fe(NO)2}9 dinitrosyl iron complex (DNIC).
Inorg Chem
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Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Nitrosylation of high-spin [Fe(κ(2)-O(2)NO)(4)](2-) (1) yields {Fe(NO)}(7) mononitrosyl iron complex (MNIC) [(κ(2)-O(2)NO)(κ(1)-ONO(2))(3)Fe(NO)](2-) (2) displaying an S = 3/2 axial electron paramagnetic resonance (EPR) spectrum (g(⊥) = 3.988 and g(∥) = 2.000).
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