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On the nature of the ‘methoxy’ cation

✍ Scribed by Willem J. Bouma; Ross H. Nobes; Leo Radom

Publisher
John Wiley and Sons
Year
1982
Tongue
English
Weight
310 KB
Volume
17
Category
Article
ISSN
1076-5174

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✦ Synopsis

Ab inifio molecular orbital calculations with large, polarization basis sets and incorporating valence-electron correlation have been used to investigate the structure of the [COH,]' ion formed at threshold from fragmentation of dimethyl ether in the mass spectrometer. The results indicate that tbis ion is the hydroxymethyl cation, [CH20H]+, formed with excess energy in a two-step rearrangement-dhociation process involving an initial 1,2-hydrogen shift in the dimethyl ether radical cation to yield an oxonium ion intermediate, [CH20HCH3]", followed by C-0 bond cleavage. The intermediate oxonium ion is predicted to lie slightly lower in energy than the dimethyl ether radical cation and represents a stable, previously unreported [C2&O]" isomer. It is suggested that at high energies, decomposition of the dmethyl ether radical cation involves dissociation followed by rearrangement.

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