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Published on: March 24, 2018
Stability of superoxide ion in imidazolium cation-based room-temperature ionic liquids
Md Mominul Islam1, Tatsuya Imase, Takeyoshi Okajima
1Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan.
Abstract:
The stability of superoxide ion (O(2)(*-)) generated chemically by dissolving KO(2) in dried dimethyl sulfoxide solutions containing imidazolium cation [e.g., 1-ethyl-3-methylimidazolium (EMI(+)) and 1-n-butyl-2,3-dimethylimidazolium (BMMI(+))] based ionic liquids (ILs) was investigated with UV-visible spectroscopic, NMR, and voltammetric techniques and an ab initio molecular orbital calculation. UV-visible spectroscopic and cyclic voltammetric measurements reveal that the O(2)(*-) species reacts with BMMI(+) and EMI(+) cations of ILs to form hydrogen peroxide. The pseudo first order rate constant for the reaction of BMMI(+) and O(2)(*-) species was found to be about 2.5 x 10(-3) s(-1). With a molecular orbital calculation, the O(2)(*-) species is understood to attack the 2-position (C-2) of the imidazolium ring (i.e., BMMI(+)) to form an ion pair complex in which one oxygen atom is bounded to C-2 and the other to the hydrogen atom of -CH(3) group attached to C-2. Eventually, the ion pair complex of BMMI(+) cation and O(2)(*-) species undergoes a ring opening reaction as evidenced with (1)H NMR measurement.
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Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Ionic Association