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

doi:10.1021/acs.organomet.1c00247

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

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

2 Citations (Scopus)

335 Downloads (Pure)

Abstract

The oxidation of [n]nickelocenophanes [Ni(η⁵-C₅H₄)₂(CH₂)₃] (3), [Ni(η^5-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 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 a chemical oxidation, and were structurally characterized. Ni−Cp_cent 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 (M_w = 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 language	English
Pages (from-to)	1945–1955
Number of pages	11
Journal	Organometallics
Volume	40
Issue number	12
Early online date	18 Jun 2021
DOIs	https://doi.org/10.1021/acs.organomet.1c00247
Publication status	Published - 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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10.1021/acs.organomet.1c00247

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Cobalt- and Nickel-based Polymetallocenes: Functional Metallopolymers from Earth-Abundant Metals
Spencer, J. (Principal Investigator)
1/10/16 → 30/09/18
Project: Research

Cite this

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title = "Redox Chemistry of Nickelocene-Based Monomers and Polymers",

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 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 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.",

author = "Musgrave, \{Rebecca A\} and Russell, \{Andrew D.\} and Gamm, \{Paul R.\} and Hailes, \{Rebekah L. N.\} and Kevin Lam and Sparkes, \{Hazel A\} and Green, \{Jennifer C.\} and Geiger, \{William E.\} and Ian Manners",

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: {\textcopyright} 2021 American Chemical Society",

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doi = "10.1021/acs.organomet.1c00247",

language = "English",

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T1 - Redox Chemistry of Nickelocene-Based Monomers and Polymers

AU - Musgrave, Rebecca A

AU - Russell, Andrew D.

AU - Gamm, Paul R.

AU - Hailes, Rebekah L. N.

AU - Lam, Kevin

AU - Sparkes, Hazel A

AU - Green, Jennifer C.

AU - Geiger, William E.

AU - Manners, Ian

N1 - 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

PY - 2021/6/28

Y1 - 2021/6/28

N2 - 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 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 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.

AB - 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 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 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.

U2 - 10.1021/acs.organomet.1c00247

DO - 10.1021/acs.organomet.1c00247

M3 - Article (Academic Journal)

SN - 0276-7333

VL - 40

SP - 1945

EP - 1955

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Redox Chemistry of Nickelocene-Based Monomers and Polymers

Abstract

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Cobalt- and Nickel-based Polymetallocenes: Functional Metallopolymers from Earth-Abundant Metals

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