A Ferrocene‐Based Dicationic Iron(IV) Carbonyl Complex. Issue 44 (2nd October 2018)

• Record Type: Journal Article
• Authors: Malischewski, Moritz; Seppelt, Konrad; Sutter, Jörg; Munz, Dominik; Meyer, Karsten
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 44(2018)
• Page Start: 14597
• Page End: 14601
• Publication Date: 2018-10-02
• Subjects: 57Fe Mössbauer spectroscopy -- carbonyl ligands -- cyclopentadienyl ligands -- iron -- metallocenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201809464
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The 16‐valence electron species [Cp*2 Fe] 2+ (Cp*=η‐C5 Me5 ), formally featuring a tetravalent iron ion, quantitatively binds CO in HF solution to form the stable, diamagnetic carbonyl species [Cp*2 Fe(CO)] 2+ . This dication forms salts in the presence of AsF6 − and SbF6 − that were crystallographically characterized. The molecular structure in crystals of [Cp*2 Fe(CO)](AsF6 )2 displays cyclopentadienyl rings that are clearly not parallel and an equatorially bound η 1 ‐CO ligand. The formal oxidation state +IV of iron was investigated by 57 Fe Mössbauer spectroscopy and is supported by DFT computational analysis. A detailed spectroscopic characterization of the hitherto unprecedented high‐valent iron carbonyl compounds is reported. Abstract : The classical iron carbonyl complex [Cp*2 Fe(CO)](AsF6 )2, containing formally tetravalent iron, has been prepared by treating [Cp*2 Fe] 2+ with carbon monoxide in anhydrous HF. The complex was characterized by various spectroscopic techniques, including 57 Fe Mössbauer spectroscopy and DFT computational analysis.