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Bielawski, Christopher W.
Synthetic Materials & Macromolecules
Research Interests
  • Synthetic chemistry, materials science, polymer chemistry, catalysis, carbon-based materials

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Potentiostatically Controlled Olefin Metathesis

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Title
Potentiostatically Controlled Olefin Metathesis
Author
Ahumada, GuillermoRyu, YeonkyeongBielawski, Christopher W.
Issue Date
2020-05
Publisher
AMER CHEMICAL SOC
Citation
ORGANOMETALLICS, v.39, no.10, pp.1744 - 1750
Abstract
A Ru(II) complex supported by an N-heterocyclic carbene annulated to a redox-active naphthoquinone (NQ) was interrogated using a range of potentiodynamic and potentiostatic electrochemical techniques. The complex exhibited two redox processes, one of which was attributed to the Ru(II)IRu(III) couple (E-1/2 = +1.10 V vs a saturated calomel electrode) and the other to the NQJNIQ(-) couple (E-1/2 = -0.62 V). Using potentiostatic coulometry or bulk electrolysis, the application of a fixed negative potential (-0.9S V) to electrodes placed in a dichloromethane solution containing the complex resulted in a reduction reaction. The complex was quantitatively reduced within minutes, as determined by coulometry, and subsequently oxidized to its initial, neutral form through the application of a relatively positive potential (+0.34 V) over similar periods of time. The interconversion process was found to be reversible and used to modulate a series of ring-closing metathesis and ring-opening metathesis polymerization reactions. While relatively high activities were observed when the neutral form of the catalyst was employed, the reaction rates were attenuated upon in situ, potentiostatic reduction. Toggling between relatively negative or positive potentials enabled the aforementioned olefin metathesis reactions to be switched between fast and slow states.
URI
https://scholarworks.unist.ac.kr/handle/201301/49130
URL
https://pubs.acs.org/doi/abs/10.1021/acs.organomet.0c00052
DOI
10.1021/acs.organomet.0c00052
ISSN
0276-7333
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CHM_Journal Papers
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