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

被引：7

作者：

Wittrig, Ashley M. ^{[1
]}

Archibold, Enada F. ^{[1
]}

Sheng, Huaming ^{[1
]}

Nash, John J. ^{[1
]}

Kenttaemaa, Hilkka I. ^{[1
]}

机构：

[1] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA

来源：

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY | 2015年 / 377卷

基金：

美国国家卫生研究院;

关键词：

Dual-linear quadrupole ion trap; Ion-molecule reactions; Reactivity; para-Benzynes; Enediynes; Mass spectrometry; DISTONIC RADICAL CATIONS; QUADRUPOLE ION-TRAP; REACTION EFFICIENCIES; META-BENZYNE; P-BENZYNE; CHEMISTRY; ISOMERS; MODEL;

D O I：

10.1016/j.ijms.2014.04.017

中图分类号：

O64 [物理化学（理论化学）、化学物理学]; O56 [分子物理学、原子物理学];

学科分类号：

070203 ; 070304 ; 081704 ; 1406 ;

摘要：

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 reacts 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. (C) 2014 Elsevier B.V. All rights reserved.

引用

页码：39 / 43

页数：5