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Herein, the synthesis of ferrocene-containing salts is presented. Acylation of ferrocene (Fc) according to the Friedel–Crafts method led to ω-bromoacyl ferrocenes. The ω-bromoacyl ferrocenes were subsequently introduced to quaternization reaction with tri-tert-butyl phosphine, which resulted in phosphonium salts. Obtained phosphonium salts were characterized by physical methods. The electrochemical properties of phosphonium salts were studied by cyclic voltammetry (CV). It was found that the replacement of n-butyl fragments at the phosphorus atom by tert-butyl leads to a more anodic potential shift. In contrast to isolobal structures Fc-C(O)(CH2)nP+(n-Bu)3X− and Fc-(CH2)n+1P+(n-Bu)3X−, the CV curves of Fc-C(O)(CH2)nP+(t-Bu)3X− and Fc-(CH2)n+1P+(t-Bu)3X− did not show a large discrepancy between forward and reverse currents. The transformation of the C=O groups to CH2 fragments had a significant effect on the electrochemical properties of ferrocene salts, the oxidation potential of which is close to that of pure ferrocene. [ABSTRACT FROM AUTHOR]

A diglyme solution of Na[cyclo‐P5] (1) reacts with alkynes and isolobal nitriles and phosphaalkynes to afford the otherwise elusive (aza)phospholide anions 2 a–c, 4 a,b, and 6. The reaction of Na[cyclo‐P5] with alkynes and nitriles was studied by means of DFT methods, which suggested a concerted mechanism for the formation of 2 a and 4 b. The anions 2 a–c, 4 a,b, and 6 coordinate in an η5‐fashion towards FeII to give the sandwich (aza)phosphametallocenes 3 a–c, 5 a,b and 7 in moderate to good yields. The new compounds were characterized by means of multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction and cyclic voltammetry. [ABSTRACT FROM AUTHOR]