The one-electron reduction of a diiron cationic complex revealed unique features: cleavage of the diiron structure occurred despite a multidentate bridging C3 ligand and was accompanied by the clean dissociation of one n5-cyclopentadienyl ring and one iron as isolated units. Thus, the iron(II)-iron(II) μ-vinyliminium complex [Fe2Cp2(CO)(μ-CO)μ- n 1: n 3-C3(Et)C2HC1N(Me)(Xyl)][SO3CF3] ([1a]SO3CF3) reacted with cobaltocene in tetrahydrofuran (THF), affording the iron(II) vinylaminoalkylidene [FeCp(CO)C1N(Me)(Xyl)C2HC3(Et)C(=O)] (2a) in 77% yield relative to the C3 ligand. Analogously, [FeCp(CO)C1N(Me)(Xyl)C2HC3(CH2OH)C(=O)] (2b) was obtained in 64% yield from the appropriate diiron precursor and CoCp2. The formation of 2a is initiated by the one-electron reduction of [1a]+, followed by a reversible intramolecular rearrangement terminating with the irreversible release of CpH (NMR and gas chromatography-mass spectrometry) and Fe [electron paramagnetic resonance (EPR) and magnetometry]. The key intermediate iron(I) ferraferrocene (3) was detected by EPR and IR spectroelectrochemistry, while the related species 3-H-3 was isolated after the addition of a hydrogen source and then identified by X-ray diffraction. A plausible mechanism for the route from [1a]+ to 3 was ascertained by density functional theory calculations. The dication [1a]2+, displaying both carbonyl ligands in terminal positions, and the anion [3]- were electrochemically generated. The functionalized diiron compounds 4 (52% yield) and 5 (62%) were afforded through the activation of O2 and S8 by a radical intermediate along the reductive pathway of [1a]+. The reaction of [Fe2Cp2(CO)(μ-CO)μ- n 1: n 3-C(SiMe3)CHCN(Me)(Xyl)][SO3CF3] ([1c]SO3CF3) with CoCp2 in THF afforded [Fe2Cp2(C≡CSiMe3)(CO)(μ-CO)μ-CNMe(Xyl)] (6) in 65% yield.

Controlled Dissociation of Iron and Cyclopentadienyl from a Diiron Complex with a Bridging C3 Ligand Triggered by One-Electron Reduction

Agonigi, Gabriele;Ciancaleoni, Gianluca;Funaioli, Tiziana;Pineider, Francesco;Pampaloni, Guido;Marchetti, Fabio
2018-01-01

Abstract

The one-electron reduction of a diiron cationic complex revealed unique features: cleavage of the diiron structure occurred despite a multidentate bridging C3 ligand and was accompanied by the clean dissociation of one n5-cyclopentadienyl ring and one iron as isolated units. Thus, the iron(II)-iron(II) μ-vinyliminium complex [Fe2Cp2(CO)(μ-CO)μ- n 1: n 3-C3(Et)C2HC1N(Me)(Xyl)][SO3CF3] ([1a]SO3CF3) reacted with cobaltocene in tetrahydrofuran (THF), affording the iron(II) vinylaminoalkylidene [FeCp(CO)C1N(Me)(Xyl)C2HC3(Et)C(=O)] (2a) in 77% yield relative to the C3 ligand. Analogously, [FeCp(CO)C1N(Me)(Xyl)C2HC3(CH2OH)C(=O)] (2b) was obtained in 64% yield from the appropriate diiron precursor and CoCp2. The formation of 2a is initiated by the one-electron reduction of [1a]+, followed by a reversible intramolecular rearrangement terminating with the irreversible release of CpH (NMR and gas chromatography-mass spectrometry) and Fe [electron paramagnetic resonance (EPR) and magnetometry]. The key intermediate iron(I) ferraferrocene (3) was detected by EPR and IR spectroelectrochemistry, while the related species 3-H-3 was isolated after the addition of a hydrogen source and then identified by X-ray diffraction. A plausible mechanism for the route from [1a]+ to 3 was ascertained by density functional theory calculations. The dication [1a]2+, displaying both carbonyl ligands in terminal positions, and the anion [3]- were electrochemically generated. The functionalized diiron compounds 4 (52% yield) and 5 (62%) were afforded through the activation of O2 and S8 by a radical intermediate along the reductive pathway of [1a]+. The reaction of [Fe2Cp2(CO)(μ-CO)μ- n 1: n 3-C(SiMe3)CHCN(Me)(Xyl)][SO3CF3] ([1c]SO3CF3) with CoCp2 in THF afforded [Fe2Cp2(C≡CSiMe3)(CO)(μ-CO)μ-CNMe(Xyl)] (6) in 65% yield.
Agonigi, Gabriele; Ciancaleoni, Gianluca; Funaioli, Tiziana; Zacchini, Stefano; Pineider, Francesco; Pinzino, Calogero; Pampaloni, Guido; Zanotti, Valerio; Marchetti, Fabio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/941340
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