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Effects of Strong Ion‐Pairing on the Electrochemical Reduction of Cyclooctatetraene in Tetrahydrofuran in the Presence of Lithium Ion. Peak Coalescence Does Not Imply Potential Inversion
Author(s) -
Fry Albert J.
Publication year - 2006
Publication title -
electroanalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.574
H-Index - 128
eISSN - 1521-4109
pISSN - 1040-0397
DOI - 10.1002/elan.200503427
Subject(s) - cyclooctatetraene , tetrahydrofuran , pairing , chemistry , ion , electrochemistry , lithium (medication) , coalescence (physics) , inorganic chemistry , computational chemistry , molecule , electrode , organic chemistry , physics , medicine , superconductivity , quantum mechanics , solvent , astrobiology , endocrinology
The first study of the voltammetric reduction of cyclooctatetraene (COT) in tetrahydrofuran (THF) in the presence of lithium ion is reported. A single wave is observed at −2.23 V vs. Ag/0.1 M AgNO 3 . Density functional calculations have been carried out on a variety of COT/Li/THF species in order to clarify the nature and role of ion pairing in this system. The dominant species in solution are the COT/Li/(THF) 2 anion radical and the COT/Li 2 /(THF) 4 dianion. Computer simulations have been carried out to further understand the effects of ion pairing on the reduction. The simulations show that coalescence of two waves into one can occur in the presence of strong ion pairing even when the second reduction potential is negative of the first.