Nitrate-to-Nitrite-to-Nitric Oxide Conversion Modulated by Nitrate-Containing {Fe(NO)2}9 Dinitrosyl Iron Complex (DNIC)
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- 作者：Fu-Te Tsai ; Yu-Ching Lee ; Ming-Hsi Chiang ; Wen-Feng Liaw
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：January 7, 2013
- 年：2013
- 卷：52
- 期：1
- 页码：464-473
- 全文大小：485K
- 年卷期：v.52,no.1(January 7, 2013)
- ISSN：1520-510X
文摘
Nitrosylation of high-spin [Fe(魏2-O2NO)4]2鈥?/b> (1) yields {Fe(NO)}7 mononitrosyl iron complex (MNIC) [(魏2-O2NO)(魏1-ONO2)3Fe(NO)]2鈥?/b> (2) displaying an S = 3/2 axial electron paramagnetic resonance (EPR) spectrum (g = 3.988 and g = 2.000). The thermally unstable nitrate-containing {Fe(NO)2}9 dinitrosyl iron complex (DNIC) [(魏1-ONO2)2Fe(NO)2]鈥?/b> (3) was exclusively obtained from reaction of HNO3 and [(OAc)2Fe(NO)2]鈥?/b> and was characterized by IR, UV鈥搗is, EPR, superconducting quantum interference device (SQUID), X-ray absorption spectroscopy (XAS), and single-crystal X-ray diffraction (XRD). In contrast to {Fe(NO)2}9 DNIC [(ONO)2Fe(NO)2]鈥?/b> constructed by two monodentate O-bound nitrito ligands, the weak interaction between Fe(1) and the distal oxygens O(5)/O(7) of nitrato-coordinated ligands (Fe(1)路路路O(5) and Fe(1)路路路O(7) distances of 2.582(2) and 2.583(2) 脜, respectively) may play important roles in stabilizing DNIC 3. Transformation of nitrate-containing DNIC 3 into N-bound nitro {Fe(NO)}6 [(NO)(魏1-NO2)Fe(S2CNEt2)2] (7) triggered by bis(diethylthiocarbamoyl) disulfide ((S2CNEt2)2) implicates that nitrate-to-nitrite conversion may occur via the intramolecular association of the coordinated nitrate and the adjacent polarized NO-coordinate ligand (nitrosonium) of the proposed {Fe(NO)2}7 intermediate [(NO)2(魏1-ONO2)Fe(S2CNEt2)2] (A) yielding {Fe(NO)}7 [(NO)Fe(S2CNEt2)2] (6) along with the release of N2O4 (路NO2) and the subsequent binding of 路NO2 to complex 6. The N-bound nitro {Fe(NO)}6 complex 7 undergoes Me2S-promoted O-atom transfer facilitated by imidazole to give {Fe(NO)}7 complex 6 accompanied by release of nitric oxide. This result demonstrates that nitrate-containing DNIC 3 acts as an active center to modulate nitrate-to-nitrite-to-nitric oxide conversion.
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