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Five-Coordinate Low-Spin {FeNO}7 PNP Pincer Complexes.
Jan Pecak1, Berthold Stöger2, Matthias Mastalir1
1Institute of Applied Synthetic Chemistry , Vienna University of Technology , Getreidemarkt 9 , A-1060 Vienna , Austria.
Researchers synthesized novel air-stable iron(I) nitrosonium PNP pincer complexes. These iron(I) complexes efficiently catalyze the N-alkylation of amines and alcohols.
Area of Science:
- Organometallic Chemistry
- Catalysis
Background:
- Iron complexes with pincer ligands are valuable in catalysis.
- Nitrosonium ligands offer unique electronic properties.
Purpose of the Study:
- To synthesize and characterize novel air-stable cationic mono nitrosonium iron(I) PNP pincer complexes.
- To investigate the electronic structure and bonding of these complexes.
- To explore their catalytic activity in N-alkylation reactions.
Main Methods:
- Direct nitrosylation of iron(II) precursors with nitric oxide.
- Magnetic and Electron Paramagnetic Resonance (EPR) measurements.
- Density Functional Theory (DFT) calculations and X-ray crystallography.
Main Results:
- Successful synthesis of air-stable cationic mono nitrosonium Fe(I) PNP pincer complexes.
- Characterization confirmed a low-spin d7 configuration and a linear NO ligand, indicating Fe(I)NO+ character.
- X-ray structures elucidated the molecular geometry of the synthesized complexes.
Conclusions:
- The synthesized iron(I) nitrosonium complexes are air-stable and possess a unique electronic configuration.
- [Fe(PNPNH-iPr)(NO)(Cl)]+ demonstrates efficient catalytic activity for mono N-alkylation of amines and alcohols.
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