Reactions of a distonic peroxyl radical anion influenced by SOMO-HOMO conversion: an example of anion-directed channel switching
Sui So, Benjamin B Kirk, Uta Wille, Adam J Trevitt, Stephen J Blanksby, Gabriel da Silva
Physical Chemistry Chemical Physics | Royal Society of Chemistry | Published : 2020
In free radicals the singly occupied molecular orbital (SOMO) typically has the highest energy. Recent examples of distonic radical anions were found, however, to disobey the usual orbital configuration, with the singly occupied molecular orbital buried energetically underneath doubly occupied orbitals. This unusual ordering of electrons, which contradicts the aufbau principle, has been characterized as SOMO–HOMO orbital conversion and is expected to perturb radical anion reactivity by branching toward anion-driven over radical-driven processes. Here, we use ion trap mass spectrometry and ab initio calculations to demonstrate that SOMO–HOMO orbital conversion influences the reactivity of a d..View full abstract
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Awarded by Australian Research Council
Support by the Australian Research Council under the Discovery Project Scheme (DP170101596) is gratefully acknowledged.