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Three new isomers of [C 2 H 6 O] + ˙: The radical cations [CH 3 O(H)CH 2 ] + ˙, [CH 3 CHOH 2 ] + ˙ and a low‐energy isomer of unassigned structure
Author(s) -
Burgers Peter C.,
Holmes John L.,
Terlouw Johan K.,
van Baar Ben
Publication year - 1985
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210200307
Subject(s) - metastability , ion , crystallography , chemistry , physics , analytical chemistry (journal) , stereochemistry , organic chemistry , chromatography
Three new [C 2 H 6 O] + ˙ ions have been generated in the gas phase by appropriate dissociative ionizations and characterized by means of their metastable and collisionally induced fragmentations. The heats of formation, Δ H f 0 , of the two ions which were assigned the structures [CH 3 O(H)CH 2 ] + ˙ and [CH 3 CHOH 2 ] + ˙ could not be measured. The third isomer, to which the structure \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 2} = \mathop {\rm C}\limits^{\rm .} {\rm H} \cdot \cdot \cdot \mathop {\rm H}\limits^ + \cdot \cdot \cdot {\rm OH}_{\rm 2} $\end{document} is tentatively assigned, was measured to have Δ H f 0 = 732±5 kJ mol −1 , making it the [C 2 H 6 O] + ˙ isomer of lowest experimental heat of formation. It was found that the exothermic ion–radical recombinations [CH 2 OH] + +CH 3 ˙→[CH 3 O(H)CH 2 ] + ˙ and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_{\rm 3} \mathop {\rm C}\limits^{\rm + } {\rm HOH + H}^{\rm .} $\end{document} →[CH 3 CHOH 2 ] + ˙ have large energy barriers, 1.4 and ⩾0.9 eV, respectively, whereas the recombinations yielding [CH 3 CH 2 OH] + ˙ have little or none.