LOCATING THE CHARGE SITE IN HETEROAROMATIC CATIONS

Citation
M. Carvalho et al., LOCATING THE CHARGE SITE IN HETEROAROMATIC CATIONS, Chemistry (Weinheim), 4(7), 1998, pp. 1161-1168
Citations number
39
Categorie Soggetti
Chemistry
Journal title
ISSN journal
09476539
Volume
4
Issue
7
Year of publication
1998
Pages
1161 - 1168
Database
ISI
SICI code
0947-6539(1998)4:7<1161:LTCSIH>2.0.ZU;2-M
Abstract
Low-energy collision-induced dissociation (CID) and ion-molecule react ions with 2-methyl-1,3-dioxolane (MD) performed by pentaquadrupole (Qq QqQ) mass spectrometry were applied to locate the charge site in isome ric heteroaromatic cations. The 2-, 3-, and 4-pyridyl cations are indi stinguishable by CID. However, as suggest ed by MS3 experiments and ab initio calculations, the 2-pyridyl cation reacts extensively with MD by a transacetalization-like mechanism to afford a bicyclic dihydrooxa zolopyridyl cation. The 3- and 4-pyridyl cations, on the contrary reac t predominantly with MD by proton transfer, as does the analogous phen yl cation. The 2-. 4-, and 5-pyrimidyl cations display characteristic CID behavior. In addition, the 2-pyrimidyl cation reacts extensively w ith MD by the transacetalization-like mechanism, whereas proton transf er occurs predominantly for the 4- and 5-pyrimidyl cations. The ions t hought to be the 2- and 3-furanyl and 2- and 3-thiophenyl cations show indistinguishable CID and ion-molecule behavior. This is most likely the result of their inherent instability in the gas phase and their sp ontaneous isomerization to the corresponding butynoyl and butynethioyl cations HC=CHCH2C=O+ and HC=CHCH2C=S+. These isomerizations, which ar e considerably exothermic according to G2(MP2) ab initio calculations, are indicated by a series of experimental results. The ions dissociat e upon CID by loss of CO or CS and undergo transacetalization with MD. Most informative is the participation of HC=CHCH2C=S+ in a transaceta lization/dissociation sequence with replacement of sulfur by oxygen, w hich is structurally diagnostic for thioacylium ions. It is therefore possible to locate the charge site of the 2-pyridyl and the three 2-, 4-, and 5-pyrimidyl cations and to identify the isomeric precursors fr om which they are derived. However, rapid isomerization to the common HC=CHCH2-C=O(S)(+) ion eliminates characteristic chemical behavior tha t could result from different charge locations in the heteroaromatic 2 - and 3-furanyl and 2- and 3-thiophenyl cations.