The vinyloxonium cation (CH2CHOH2+)

✍ Scribed by Ross H. Nobes; Leo Radom

• Book ID: 103022790
• Publisher: Elsevier Science
• Year: 1983
• Tongue: English
• Weight: 385 KB
• Volume: 99
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(83)80539-9

✦ Synopsis

Ab initio molecular orbital calculations with 1.1r~e basis sets and incorporating correlation nre used to cxarninc the structures and relative energies of the vinylownium (CH2CHOH:) and I-hpdro.\_vethyl (CH3CHOll+) cations. The best structure of the vinylo\onium ion hds the OH2 plane perpendicular to the CC0 pldnc. The energy difference between the vinyloxonium and I-hydroxyethyl cations is predicted to be 92 kJ mol-*, substantially grcdtcr than a recent experimental estimate of 41 * 12 kJ nlol-l . 1_ Intrcduction Three C,H,O+ species are well characterized as being distinct, stable isomers in the gas phase [I ] _ These are the I-hydroxyethyl cation (l), the methoxymethyl cation (2) and 0-protonated oximne (3)_ In an earlier theoretical study [ 11, we proposed that the vinyloxonium cation (4) is also likely to be an observable CZH50+ isomer because of its low relative energy and high barriers to intramolecular rearrange-ment_ In fact, Burgers, Terlouw and Holmes (BTH)