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Non-heme High-Spin {FeNO}6–8 Complexes: One Ligand Platform Can Do It All
- Source :
- Journal of the American Chemical Society. 140:11341-11359
- Publication Year :
- 2018
- Publisher :
- American Chemical Society (ACS), 2018.
-
Abstract
- Heme and non-heme iron–nitrosyl complexes are important intermediates in biology. While there are numerous examples of low-spin heme iron–nitrosyl complexes in different oxidation states, much less is known about high-spin (hs) non-heme iron–nitrosyls in oxidation states other than the formally ferrous NO adducts ({FeNO}7 in the Enemark–Feltham notation). In this study, we present a complete series of hs-{FeNO}6–8 complexes using the TMG3tren coligand. Redox transformations from the hs-{FeNO}7 complex [Fe(TMG3tren)(NO)]2+ to its {FeNO}6 and {FeNO}8 analogs do not alter the coordination environment of the iron center, allowing for detailed comparisons between these species. Here, we present new MCD, NRVS, XANES/EXAFS, and Mossbauer data, demonstrating that these redox transformations are metal based, which allows us to access hs-Fe(II)–NO–, Fe(III)–NO–, and Fe(IV)–NO– complexes. Vibrational data, analyzed by NCA, directly quantify changes in Fe–NO bonding along this series. Optical data allow for the ident...
- Subjects :
- Extended X-ray absorption fine structure
010405 organic chemistry
Ligand
Center (category theory)
General Chemistry
010402 general chemistry
01 natural sciences
Biochemistry
Redox
Catalysis
XANES
0104 chemical sciences
Metal
chemistry.chemical_compound
Crystallography
Colloid and Surface Chemistry
chemistry
visual_art
Mössbauer spectroscopy
visual_art.visual_art_medium
Heme
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 140
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi...........b216e7fbaffe83cd0ccfc5247c96728f