Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N '-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Date

2006-11-15

Author

Kocak, F. Sanem
Kavakli, Cuneyt
Akyol, Ceyhun
Önal, Ahmet Muhtar
Özkar, Saim

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Thermal substitution reaction of Cr(CO)4(η2:2-1,5-cyclooctadiene), Mo(CO)4(η2:2-norbornadiene), and W(CO)5(η2-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)4(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)5(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)4(bfeda). The electrochemical behavior of the M(CO)4(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH2Cl2 solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)4(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)4(bfeda) and W(CO)4(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.

Subject Keywords

Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Materials Chemistry, Biochemistry

URI

https://hdl.handle.net/11511/34680

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY

DOI

https://doi.org/10.1016/j.jorganchem.2006.08.079

Collections

Department of Chemistry, Article

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Citation Formats

F. S. Kocak, C. Kavakli, C. Akyol, A. M. Önal, and S. Özkar, “Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N ’-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes,” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 5030–5037, 2006, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/34680.