TY  - JOUR
AB  - The reaction of Me2F+, Me2C1+ and CF3+ with p-Me3CC6H4(CH2)n,C6D5 (n = 2, 3) initiates a reaction pattern whose major features are accounted for by the additional electrostatic stabilization afforded by the second (spectator) aromatic ring on ionic intermediates and ion-molecule complexes. The Me3C loss following CX3- (X = H, F) addition to the tert-butyl-substituted ring is significantly reduced with respect to a single-ring model substrate, p-Me3CC6H4Me. [Arene · Me3C+] non-covalent complexes mediate the observed interannular and intermolecular Me3C+ transfer. Unimolecular cleavage of Me3CH from [arene · Me3C+], following side-chain H- abstraction, a major fragmentation pathway under mass spectrometric conditions, is instead largely inhibited in the reported radiolytic experiments. Such behavior is accounted for by the effective stabilization of ion-molecule non-covalent complexes ensured by unreactive collisions with about 1 atm bath gas.
DA  - 1995
DO  - 10.1016/0168-1176(95)04249-K
KW  - Ion-neutral complexes
KW  - Arenium ions
KW  - Interannular carbenium ion migration
KW  - Isomerization
LA  - eng
IS  - 3
M2  - 215
PY  - 1995
SN  - 0168-1176
SP  - 215-228
T2  - International Journal of Mass Spectrometry and Ion Processes
TI  - [Arene Me3C+] non-covalent complexes in the gas-phase (trifluoro)methylation of tert-butyl-substituted diphenylalkanes
UR  - https://nbn-resolving.org/urn:nbn:de:0070-pub-17741727
Y2  - 2024-11-21T17:11:08
ER  -