The unimolecular chemistry of [1,2-propanediol]+˙: a rationale in terms of hydrogen-bridged radical cations |
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Authors: | Ben L. M. Van Baar Peter C. Burgers John L. Holmes Johan K. Terlouw |
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Abstract: | By combining results from a variety of mass spectrometric techniques (metastatle ion, collisional activation, collision-induced dissociative ionization, neutralization–reionization spectrometry and appearance energy measurements) and the classical method of isotopic labelling, a unified mechanism is proposed for the complex unimolecular chemistry of ionized 1,2-propanediol. The key intermediates involved are the stable hydrogen-bridged radical cations [CH2?C(H)? H…?O…?O(H)CH3]+˙, which were generated independently from [4-methoxy, 1-butanol]+˙ (loss of C2H4) and [1-methoxyglycerol]+˙ (loss of CH2O), [CH3? C?O…?H…?O(H)CH3]+˙ and the related ion-dipole complex [CH2?C(OH)CH3/H2O]+˙. The latter species serves as the precursor for the loss of CH3˙ and in this reaction the same non-ergodic behaviour is observed as in the loss of CH3˙ from the ionized enol of acetone. |
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