TY - JOUR
T1 - Solution-phase energy profiles for trigonal bipyramidal species postulated as intermediates for the hydrolysis of methyl ethylene phosphate
AU - Uchimaru, T.
AU - Kawahara, S.
AU - Tsuzuki, S.
AU - Matsumura, K.
AU - Taira, K.
PY - 1999/9/1
Y1 - 1999/9/1
N2 - We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.
AB - We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.
KW - Ab initio and DFT calculations
KW - Hydrolysis of methyl ethylene phosphate
KW - Pseudorotation
KW - Solution-phase reaction profile
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U2 - 10.1016/S0166-1280(99)00072-X
DO - 10.1016/S0166-1280(99)00072-X
M3 - Article
AN - SCOPUS:0033198357
VL - 469
SP - 215
EP - 221
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 1-3
ER -