Ferrocene-Containing Sterically Hindered Phosphonium Salts

Abstract

The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br− anion by [BF4]− shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br− anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br− ion compared to BF4− are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.

Conductive Mediators in Oxidation Based on Ferrocene Functionalized Phosphonium Ionic Liquids

“…Due to unique physical properties such as high conductivity, a very wide electrochemical window, stability, and reproducibility, phosphonium IL with sterically hindered cation was successfully applied in an electrochemical study of insoluble compounds [ 27 , 28 ]. Recently, we reported the synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di( tert -butyl)ferrocenyl phosphine [ 29 , 30 ]. In development of this concept, we extended the series of ferrocene-containing phosphonium salts, where the ferrocene fragment and the phosphorus atom are linked by a spacer of different length and nature.…”