Use of the TCNQF 4 2- Dianion in the Spontaneous Redox Formation of [Fe III (L - ) 2 ][TCNQF 4 ⋅- ].

Autor: Gass IA; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia.; School of Pharmacy and Biomolecular Sciences, University of Brighton, Brighton, BN2 4GJ, United Kingdom., Lu J; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Asadi M; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Lupton DW; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Forsyth CM; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Geoghegan BL; School of Pharmacy and Biomolecular Sciences, University of Brighton, Brighton, BN2 4GJ, United Kingdom., Moubaraki B; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Cashion JD; School of Physics and Astronomy, Monash University, Clayton, VIC, 3800, Australia., Martin LL; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Bond AM; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia., Murray KS; School of Chemistry, Monash University, Clayton, VIC, 3800, Australia.
Jazyk: angličtina
Zdroj: ChemPlusChem [Chempluschem] 2018 Jul; Vol. 83 (7), pp. 658-668. Date of Electronic Publication: 2018 Mar 09.
DOI: 10.1002/cplu.201800010
Abstrakt: The reaction of [Fe II (L . ) 2 ](BF 4 ) 2 with Li 2 TCNQF 4 results in the formation of [Fe III (L - ) 2 ][TCNQF 4 . - ] (1) where L . is the radical ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N-oxide and TCNQF 4 is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. This has been characterised by X-ray diffraction, Raman and Fourier transform infrared (FTIR) spectroscopy, variable-temperature magnetic susceptibility, Mössbauer spectroscopy and electrochemistry. X-ray diffraction studies, magnetic susceptibility measurements and Raman and FTIR spectroscopy suggest the presence of low-spin Fe III ions, the anionic form (L - ) of the ligand and the anionic radical form of TCNQF 4 ; viz. TCNQF 4 . - . Li 2 TCNQF 4 reduces the [Fe II (L . ) 2 ] 2+ dication, which undergoes a reductively induced oxidation to form the [Fe III (L - ) 2 ] + monocation resulting in the formation of [Fe III (L - ) 2 ][TCNQF 4 . - ] (1), the electrochemistry of which revealed four well-separated, diffusion-controlled, one-electron, reversible processes. Mössbauer spectroscopy and electrochemical measurements suggest the presence of a minor second species, likely to be [Fe II (L . ) 2 ][TCNQF 4 2- ].
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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