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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 21, Number 8
BKCSDE 21(8)
August 20, 2000 

Theoretical Studies on Gas-Phase Reactions of Negative Ions with Alkyl Nitrites
Hyung Yeon Park, Chan Kyung Kim, Bon-Su Lee, Hai Whang Lee, Ikchoon Lee*
Gas-Phase reactions of methyl and ethyl nitrites with anionic nucleophiles of SH-, F- and OH- are investigated theoretically at the MP2/6-311+G* level. The SN2 processes are all highly exothermic and proceed with a typ-icaI double-weIl reaction coordinate profile. The elimination reactions of methyl nitrite with SH- and F- are double-well energy surface processes,with stabilizedproduct complexes of NO-...H2S and NO-...HF, pro-ceeding by an E1 cb-like E2 mechanism. The β-elimination of ethyl nitrite is an E2 type process. The α-elimi-nation reactions of methyl and ethyl nitrites with OH- have triple-well energy profiles of Elcb pathway with an α-carbanion intermediate which is stabilized bythe vicinal ncα-б*o-N charge transfer interactions. CompIex-ation ofmethyl carbanion with HF seems to provide a stable intermediate within a triple-well energy profile of El cb channel in the reaction of F- with methyl nitrite.
823 - 827
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