The gas-phase reactivity of charged para-benzynes is entirely unexplored as they and/or their precursors tend to undergo ring-opening upon their generation. We report here a gas-phase reactivity study of two such benzynes, the 2,5-didehydropyridinium and 5,8-didehydroisoquinolinium cations, generated in a modified dual-linear quadrupole ion trap (DLQIT) mass spectrometer. Both biradicals were found to form diagnostic products with organic molecules, indicating the presence of two radical sites. As opposed to earlier predictions that the singlet-triplet (S-T) splitting controls the radical reactivity of such species, the 2,5-didehydropyridinium cation was found to react much faster in spite of its larger S-T splitting. Calculated vertical electron affinities of the radical sites of the para-benzynes, a parameter related to the polarity of the transition states of their reactions, appears to be the most important reactivity controlling factor.?

Polar effects control the gas-phase reactivity of charged <i>?para</i>?-benzyne analogs

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Polar effects control the gas-phase reactivity of charged ?para?-benzyne analogs