A mononuclear nonheme {FeNO}(6) complex: synthesis and structural and spectroscopic characterization
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Hong, Seungwoo; Karmalkar, Deepika G.; Kim, Jin; Lee, Yong-Min; Goo, Yire; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Hong, Seungwoo] Sookmyung Womens Univ, Dept Chem, Seoul 04310, South Korea; [Yan, James J.; Sutherlin, Kyle D.; Hodgson, Keith O.; Solomon, Edward I.] Stanford Univ, Dept Chem, Stanford, CA 94305 USA; [Mascharak, Pradip K.] Univ Calif Santa Cruz, Dept Chem & Biochem, Santa Cruz, CA 95064 USA; [Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.] Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA; [Karlin, Kenneth D.] Johns Hopkins Univ, Dept Chem, Charles & 34th St, Baltimore, MD 21218 USA; [Nam, Wonwoo] Shaanxi Normal Univ, Sch Chem & Chem Engn, Xian 710119, Shaanxi, Peoples R China
- 등재 SCIE, SCOPUS
- 발행기관 ROYAL SOC CHEMISTRY
- 발행년도 2018
- URI http://www.dcollection.net/handler/ewha/000000155659
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/c8sc01962b
초록/요약
While the synthesis and characterization of {FeNO}(7,8,9) complexes have been well documented in heme and nonheme iron models, {FeNO}(6) complexes have been less clearly understood. Herein, we report the synthesis and structural and spectroscopic characterization of mononuclear nonheme {FeNO}(6) and iron(iii)-nitrito complexes bearing a tetraamido macrocyclic ligand (TAML), such as [(TAML)Fe-III(NO)](-) and [(TAML)Fe-III(NO2)](2-), respectively. First, direct addition of NO(g) to [Fe-III(TAML)](-) results in the formation of [(TAML)Fe-III(NO)](-), which is sensitive to moisture and air. The spectroscopic data of [(TAML)Fe-III(NO)](-), such as H-1 nuclear magnetic resonance and X-ray absorption spectroscopies, combined with computational study suggest the neutral nature of nitric oxide with a diamagnetic Fe center (S = 0). We also provide alternative pathways for the generation of [(TAML)Fe-III(NO)](-), such as the iron-nitrite reduction triggered by protonation in the presence of ferrocene, which acts as an electron donor, and the photochemical iron-nitrite reduction. To the best of our knowledge, the present study reports the first photochemical nitrite reduction in nonheme iron models.
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