Oxidatively stable ferrocenyl-π-bridge-titanocene D-π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states

Dalton Transactions : an International Journal of Inorganic Chemistry
Jared A PienkosPaul S Wagenknecht

Abstract

The synthesis, spectroscopic, and electrochemical characterization of oxidatively stable D-π-A compounds of the form (Me2CpC2Fc)2TiCl2 and RCp2Ti(C2Fc)2CuX (where Fc = ferrocenyl) are reported. Oxidative stability enabled by the addition of CuX is evidenced by voltammagrams of the RCp2Ti(C2Fc)2CuX compounds which all display two chemically-reversible 1e- FeIII/II couples, indicative of electronic communication between the Fc- termini. Differential pulse voltammetry (DPV) in CH2Cl2/[n-Bu4N][PF6], demonstrated that the redox potential difference between the two 1e- FeIII/II couples (ΔE1/2) is between 112 mV and 146 mV, being most pronounced with the electron rich Cp*2Ti(C2Fc)2CuBr. The ΔE1/2 values were unaffected by solvent (THF) and displayed only a small dependence on the identity of the counterion, either PF6- or B(C6F5)4-. For each complex with a measurable ΔE1/2 value, spectroelectrochemical experiments were performed in CH2Cl2/[n-Bu4N][PF6] and gave clear evidence of both the one-electron oxidized mixed-valent (MV) state and the two-electron oxidized state, each with distinct spectroscopic signatures. The MV states of these complexes showed absorbance between 820 and 940 nm which were replaced with a higher energy feature ...Continue Reading

References

Jul 6, 2001·Journal of the American Chemical Society·H ImahoriS Fukuzumi
Jun 20, 2002·Journal of the American Chemical Society·Frédéric BarrièreRichard Sanders
Dec 16, 2010·Journal of the American Chemical Society·Abdou K DialloDidier Astruc
Oct 16, 2014·Chemical Society Reviews·C SchubertD M Guldi
Mar 31, 2015·Macromolecular Rapid Communications·Tae-Dong Kim, Kwang-Sup Lee
Oct 27, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Noah C VieiraPaul S Wagenknecht
May 8, 2018·Journal of the American Chemical Society·Eric J PiechotaGerald J Meyer

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Citations

May 10, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Lin-Tao ZhangTian-Lu Sheng
Oct 30, 2020·Acta Crystallographica. Section E, Crystallographic Communications·Jackson S McCarthyPaul S Wagenknecht
Jan 28, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Elizabeth S CarltonPaul S Wagenknecht

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BETA
column chromatography
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