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Redox chemistry of nickelocene-based monomers and polymers

Redox chemistry of nickelocene-based monomers and polymers

Musgrave, Rebecca A., Russell, Andrew D., Hailes, Rebekah L. N., Gamm, Paul R., Lam, Kevin ORCID: 0000-0003-1481-9212, Sparkes, Hazel A and Green, Jen (2021) Redox chemistry of nickelocene-based monomers and polymers. Organometallics, 40 (12). pp. 1945-1955. ISSN 0276-7333 (doi:https://doi.org/10.1021/acs.organomet.1c00247)

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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 in dichloromethane was also investigated by CV. The [n]nickelocenophanes 3 and 10–12 exhibited two single-electron Nernstian redox processes, and the monocations [3]+, [10]+, [11]+, and [12]+ were isolable as [B(C6F5)4]− salts after 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 partially chemically reversible.

Item Type: Article
Uncontrolled Keywords: electrochemistry, organometallics
Subjects: Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science
Faculty of Engineering & Science > School of Science (SCI)
Last Modified: 29 Jul 2021 08:38
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
Selected for GREAT 2019: None
Selected for REF2021: None
URI: http://gala.gre.ac.uk/id/eprint/33248

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