Heteroaryl oxenium ions have diverse and unusual low-energy electronic states

Patrick J. Hanway, Arthur H. Winter

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

The electronic state orderings and energies of heteroaryl oxenium ions were computed using high-level CASPT2//CASSCF computations. We find that these ions have a number of diverse, low-energy configurations. Depending on the nature of the heteroaryl substituent, the lowest-energy configuration may be open-shell singlet, closed-shell singlet, or triplet, with further diversity found among the subtypes of these configurations. The 2- and 3-pyridinyl oxenium ions show small perturbations from the phenyl oxenium ion in electronic state orderings and energies, having closed-shell singlet ground states with significant gaps to an n,π* triplet state. In contrast, the 4-pyridinyl oxenium ion is computed to have a low-energy nitrenium ion-like triplet state. The pyrimidinyl oxenium ion is computed to have a near degeneracy between an open-shell singlet and triplet state, and the pyrizidinyl oxenium ion is computed to have a near-triple degeneracy between a closed-shell singlet state, an open-shell singlet state, and a triplet state. Therefore, the ground state of these latter heteroaryl oxenium ions cannot be predicted with certainty; in principle, reactivity from any of these states may be possible. These systems are of fundamental interest for probing the spin- and configuration-dependent reactivity of unusual electronic states for this important class of reactive intermediate.

Original languageEnglish (US)
Pages (from-to)9398-9403
Number of pages6
JournalJournal of Physical Chemistry A
Volume116
Issue number37
DOIs
StatePublished - Sep 20 2012

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