Redox Chemistry of Nickelocene-Based Monomers and Polymers

Rebecca A Musgrave*, Andrew D. Russell, Paul R. Gamm, Rebekah L. N. Hailes, Kevin Lam, Hazel A Sparkes, Jennifer C. Green, William E. Geiger*, Ian Manners*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

Abstract

The oxidation of [n]nickelocenophanes [Ni(η5-C5H4)2(CH2)3] (3), [Ni(η5-C5H4)2(SiMe2)2] (10), [Ni(η5-C5H4)2(SiMe2)2O] (11), [Ni(η5-C5H4)2(CH2)4] (12), and poly (nickelocenylpropylene) [Ni(η5-C5H4)2(CH2)3]n (4) to both the monocationic and dicationic species was investigated in dichloromethane by cyclic voltammetry (CV) and square-wave voltammetry.  The presence of acetonitrile on the oxidation potentials of 3 indichloromethane was also investigated by CV. The [n]-nickelocenophanes 3 and 1012 exhibited two single-electron Nernstian redox processes, and the monocations [3]+, [10]+,[11]+, and [12]+ were isolable as [B(C6F5)4] salts, after a chemical oxidation, and were structurally characterized. Ni−Cpcent distances in all four monomers decreased upon oxidation, with a structural distortion manifested in the ring-tilt angle, α, among other angles. CV studies of the reversible first oxidation process to the polyelectrolyte {[Ni(η5-C5H4)2(CH2)3]+}n ([4]n+) were used to estimate the molecular weight of the polymeric material (Mw = 5300 g mol−1) by comparing its diffusion coefficient with that of a monomeric analogue, and the second electrochemical oxidation of polymer 4 was found to be only quasi-reversible.
Original languageEnglish
Pages (from-to)1945–1955
Number of pages11
JournalOrganometallics
Volume40
Issue number12
Early online date18 Jun 2021
DOIs
Publication statusPublished - 28 Jun 2021

Bibliographical note

Funding Information:
We thank the Engineering and Physical Sciences Research Council (EPSRC, EP/N030702/1) for funding. I.M. thanks the Government of Canada for a C150 Research Chair and the University of Bristol for support. W.E.G. thanks the National Science Foundation for support (NSF CHE-1565541).

Publisher Copyright:
© 2021 American Chemical Society

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