TY - JOUR
T1 - The formation and characterization of three-membered ring carbanions in the gas phase
T2 - An experimental and theoretical investigation of the conjugate bases of thiirane, thiirane S-oxide, and thiirane S,S-dioxide
AU - Merrill, Grant N.
AU - Zoller, Uri
AU - Reed, Dana R.
AU - Kass, Steven R.
PY - 1999/10/1
Y1 - 1999/10/1
N2 - Deprotonation of thiirane, thiirane S-oxide, and thiirane S,S-dioxide was carried out in the gas phase, and the resulting anions were studied through a series of ion-molecule reactions. The cyclic conjugate bases of thiirane (1b) and thiirane S,S-dioxide (3a) are formed whereas a facile ring opening isomerization to vinyl sulfenate anion (2d, CH2=CHSO-) is observed in the thiirane S-oxide case. Vinyl thiolate, the rearrangement product of the conjugate base of thiirane, also is obtained. Proton affinities were determined for 1b, 2d, and 3a. High-level ab initio calculations were also carried out, and the results compared with those obtained from experiment. Orbital arguments are advanced to explain the relative barriers to ring opening for the three anions of interest.
AB - Deprotonation of thiirane, thiirane S-oxide, and thiirane S,S-dioxide was carried out in the gas phase, and the resulting anions were studied through a series of ion-molecule reactions. The cyclic conjugate bases of thiirane (1b) and thiirane S,S-dioxide (3a) are formed whereas a facile ring opening isomerization to vinyl sulfenate anion (2d, CH2=CHSO-) is observed in the thiirane S-oxide case. Vinyl thiolate, the rearrangement product of the conjugate base of thiirane, also is obtained. Proton affinities were determined for 1b, 2d, and 3a. High-level ab initio calculations were also carried out, and the results compared with those obtained from experiment. Orbital arguments are advanced to explain the relative barriers to ring opening for the three anions of interest.
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U2 - 10.1021/jo9906227
DO - 10.1021/jo9906227
M3 - Article
AN - SCOPUS:0033214258
SN - 0022-3263
VL - 64
SP - 7395
EP - 7406
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 20
ER -