| dc.description | Multiple stage MS2 and MS3 mass spectrometric experiments, performed using a pentaquadrupole instrument, are employed to explore the gas-phase ion-molecule chemistry of several nitrilium [R-C=N+-H (1), R-C=N+-CH3 (2), and H-C=N+-C2H5 (3)] as well as immonium ions RR1C=N+R2R3 (4) with the neutral diene isoprene. Polar [4 + 2+] Diels-Alder cycloaddition is observed for nitrilium ions when the energy gap between the lowest unoccupied molecular orbital (LUMO) of the ion and the highest occupied molecular orbital (HOMO) of the isoprene is small and the competing proton transfer reaction is endothermic. Thus, C-protonated methyl isonitrile H-C=N+-CH3 (2a) and its higher homolog H-C=N+-C2H5 (3a) form abundant [4 + 2+] cycloadducts with isoprene, but several protonated nitriles 1 do not; instead they show exothermic proton transfer as the main ion-molecule reaction. Replacement of the methyne hydrogen in 2a by a methyl, ethyl, or phenyl group (2b-d) raises the LUMO-HOMO gap, which greatly decreases the total yield of ion-molecule products and precludes cycloaddition. On the other hand, the electron-withdrawing acetyl and bromine substituents in 2e and 2f substantially lower the LUMO energy of the ions and cycloaddition reaction occurs readily. The simplest member of the immonium ion series, CH2 = NH2+ (4a), reacts readily by cycloaddition, whereas alkyl substitution on either the carbon or nitrogen (4b-f) dramatically lowers the overall reactivity, which substantially decreases or even precludes cycloaddition. In strong contrast, the N-phenyl (4g) and N-acetyl (4h) ions and the N-vinyl-substituted immonium ion, N-protonated 2-aza-butadiene (4i), react extensively with isoprene, mainly by [4 + 2+] cycloaddition. However, the isomeric C-vinyl-substituted ion (4j) displays only modest reactivity in both the proton-transfer and the cycloaddition channels. Collision-induced dissociation (CID) of the cycloadducts performed by on-line MS3 experiments demonstrates that they are covalently bound and supports their assignments as cycloaddition products. Retro Diels-Alder fragmentation is a major process for cycloadducts of both the immonium and the nitrilium ions, but other fragmentation processes also are observed. The cycloadduct of 4a with butadiene displays CID fragmentation identical to that of the authentic ion produced by protonation of 1,2,3,6-tetrahydropyridine, which thus strengthens the [4 + 2+] cycloaddition proposal. AM1 calculations also support the formation of the [4 + 2+] cycloadducts, which are shown in several cases to be much more stable than the products of simple addition, that is, the ring-open isomers. | |
