Nitric oxide as a non-innocent ligand in (bio-)inorganic complexes: Spin and electron transfer in FeIINO bond
| Autor: | Mariusz Radoń, Ewa Broclawik, Adam Stępniewski |
|---|---|
| Rok vydání: | 2014 |
| Předmět: |
$\{Fe-NO\}^7$ complexes
Electron density Bent molecular geometry Ligands Nitric Oxide 010402 general chemistry 01 natural sciences Biochemistry donation and backdonation Adduct natural orbitals for chemical valence Inorganic Chemistry Electron transfer Atomic orbital Computational chemistry Ferrous Compounds Valence (chemistry) 010405 organic chemistry Chemistry Bond formation Non-innocent ligand 0104 chemical sciences Crystallography Models Chemical Quantum Theory charge transfer resolution Oxidation-Reduction |
| Zdroj: | Journal of Inorganic Biochemistry |
| ISSN: | 0162-0134 |
| DOI: | 10.1016/j.jinorgbio.2014.01.010 |
| Popis: | The nature of electron density transfer upon bond formation between NO ligand and Fe(II) center is analyzed on the basis of DFT calculation for two {Fe–NO} 7 complexes with entirely diverse geometric and electronic structures: Fe II P(NH 3 )NO (with bent Fe–N–O unit) and [Fe II (H 2 O) 5 (NO)] 2+ (with linear Fe–N–O structure). Proper identification of an electronic status of the fragments, “prepared” to make a bond, was found necessary to get meaningful resolution of charge and spin transfer processes from a spin-resolved analysis of natural orbitals for chemical valence. The Fe II P(NH 3 )NO adduct (built of NO 0 (S = 1/2) and Fe II P(NH 3 ) (S = 0) fragments) showed a strong π*-backdonation competing with spin transfer via a σ-donation, yielding significant red-shift of the NO stretching frequency. [Fe II (H 2 O) 5 (NO)] 2+ (built of NO 0 (S = 1/2) antiferromagnetically coupled to Fe II (H 2 O) 5 (S = 2) fragment) gave no noticeable charge or spin transfer between fragments; a slight blue-shift of the NO stretching frequency could be related to a residual π-donation due to weak π-bonding. |
| Databáze: | OpenAIRE |
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