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• W2014093075 abstract "Abstract The unimolecular gas-phase chemistry of the cyclic title ion, [OCH 2 CH 2 O]P(H)O + , 1a + , and its tautomer ethylene phosphite, [OCH 2 CH 2 O]POH + , 1b + , was investigated using mass spectrometry-based experiments in conjunction with isotopic labelling and computational quantum chemistry, at the CBS-QB3 level of theory. A facile tautomerization of the “keto” ion 1a + into its more stable (by 34 kcal/mol) “enol” isomer 1b + is prevented by a substantial 1,2-H shift barrier (14 kcal/mol relative to 1a + ). In line with this, the collision-induced dissociation (CID) and neutralization-reionization (NR) spectra of the two isomers are characteristically different. Unlike the corresponding acyclic dimethyl phosphonate/phosphite tautomers, (CH 3 O) 2 P(H)O + /(CH 3 O) 2 POH + , where the phosphonate isomer rapidly loses its structure identity by a facile distonicization into CH 2 O(CH 3 O)P(H)OH + , the barrier for this reaction in 1a + is prohibitively high and the cyclic distonic 1,2-H shift isomer [OCH 2 CH 2 O(H)]PO + , 1c + , is not directly accessible. The 1,2-H shift barrier separating 1a + and 1b + is calculated to lie close to the thermochemical threshold for the formation of C 2 H 4 + +HOP(O) 2 . This reaction dominates the closely similar metastable ion (MI) spectra of these tautomers. At these elevated energies, the “enol” ion 1b + can undergo ring-opening by CH 2 O or CH 2 CH 2 cleavage, yielding ion–dipole complexes of the type [C 2 H 4 ] + /HOP(O) 2 , 1e + , and H-bridged radical cations CH 2  O ⋯ [ H  O  P  OCH 2 ] + , 1f + , respectively. Moreover, communication of 1b + with the distonic ion 1c + now also becomes feasible. These computational findings account for the similarity of the MI spectra and provide a rationale for the observation that in the losses of CO, HCO and C 2 H 3 O from metastable ions [ OCH 2 CH 2 O ] P ( H ) 18 O + and [ OCH 2 CH 2 O ] P  18 OH + , the 18 O -atom loses its positional identity. Theory and experiment yield a consistent potential energy profile for the cyclic phosphonate/phosphite system showing that non-dissociating ions 1a + retain their structure identity in the microsecond time-frame. However, the interaction of 1a with a benzonitrile (BN) molecule in a chemical ionization type experiment readily yields the more stable “enol” type ion 1b + . Experiments with benzonitrile-d 5 support the proposal that this interaction does not involve the lowering of the 1,2-H shift barrier between the tautomers, via a proton-transport catalysis type mechanism. Rather, a “quid-pro-quo” mechanism is operative, analogous to that proposed for the benzonitrile-assisted enolization of acetamide [Int. J. Mass Spectrom. 210/211 (2001) 489]." @default.
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• W2014093075 date "2003-07-01" @default.
• W2014093075 modified "2023-09-25" @default.
• W2014093075 title "Tautomerization and dissociation of ethylene phosphonate ions [OCH2CH2O]P(H)O+: an experimental and CBS-QB3 computational study" @default.
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• W2014093075 doi "https://doi.org/10.1016/s1387-3806(03)00106-4" @default.
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