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S K-Edge X-Ray Absorption Spectroscopy and Density Functional Theory Studies of High and Low Spin {FeNO}7 Thiolate Complexes: Exchange Stabilization of Electron Delocatization in {FeNO}7 and {FeO2}8.
- Source :
-
Inorganic Chemistry . 1/17/2011, Vol. 50 Issue 2, p427-236. 10p. - Publication Year :
- 2011
-
Abstract
- S K-edge X-ray absorption spectroscopy (XAS) is a direct experimental probe of metal ion electronic structure as the pre-edge energy reflects its oxidation state, and the energy splitting pattern of the pre-edge transitions reflects its spin state. The combination of sulfur K-edge XAS and density functional theory (DFT) calculations indicates that the electronic structures of {FeNO}7 (S = 3/2) (SMe2N4(tren)Fe(NO), complex I) and {FeNO}7 (S = 1/2) ((bme-daco)Fe(NO), complex II) are FeIII(S = 5/2)-NO-(S = 1) and FeIII(S = 3/2)-NO-(S = 1), respectively. When an axial ligand is computationally added to complex II, the electronic structure becomes FeII(S = 0)-NO•(S = 1/2). These studies demonstrate how the ligand field of the Fe center defines its spin state and thus changes the electron exchange, an important factor in determining the electron distribution over {FeNO}7 and {FeO2}8 sites. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00201669
- Volume :
- 50
- Issue :
- 2
- Database :
- Academic Search Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 64289414
- Full Text :
- https://doi.org/10.1021/ic1006378