A specific gas phase substitution reaction between enol radical cations and t-butyl nitrite

Pascal Gerbaux 1 Pascale Wantier 1 Pham Cam Nam 2 Minh Tho Nguyen 2 Guy Bouchoux 3 Robert Flammang 1
1 Organic Chemistry Laboratory
2 Department of Chemistry
3 DCMR - Laboratoire des mécanismes réactionnels
Abstract : Ion-molecule reactions between ionized carbonyl compounds or ionized enols with t-butyl nitrite allow a clear-cut distinction to be made between both these isomeric structures. The most relevant difference between the observed reactions is the formal substitution of a hydrogen atom by nitric oxide in the enol ions. Collisional activation experiments on the product ions are interpreted in terms of α-nitroso carbonyl structures. However, a quantum chemical investigation at the B3LYP/6-311++G(d,p) level of theory shows that ionized α-nitroso carbonyl and vinyl nitrite structures may isomerize provided they contain ca 60 kJ mol-1 of internal energy. It is therefore possible that both structures are generated in the substitution reaction.
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Submitted on : Friday, January 10, 2014 - 9:40:49 AM
Last modification on : Wednesday, March 20, 2019 - 12:12:02 PM

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Pascal Gerbaux, Pascale Wantier, Pham Cam Nam, Minh Tho Nguyen, Guy Bouchoux, et al.. A specific gas phase substitution reaction between enol radical cations and t-butyl nitrite. European Journal of Mass Spectrometry, IM Publications, 2004, 10 (6), pp.889-898. ⟨10.1255/ejms.686⟩. ⟨hal-00926690⟩

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