Do Diradicals Behave like Radicals?

Thijs Stuyver, Bo Chen, Tao Zeng, Paul Geerlings, Frank De Proft, Roald Hoffmann

Research output: Contribution to journalReview article

Abstract

This review sets out to understand the reactivity of diradicals and how that may differ from monoradicals. In the first part of the review, we delineate the electronic structure of a diradical with its two degenerate or nearly degenerate molecular orbitals, occupied by two electrons. A classification of diradicals based on whether or not the two SOMOs can be located on different sites of the molecule is useful in determining the ground state spin. Important is a delocalized to localized orbital transformation that interchanges "closed-shell" to "open-shell" descriptions. The resulting duality is useful in understanding the dual reactivity of singlet diradicals. In the second part of the review, we examine, with a consistent level of theory, activation energies of prototypical radical reactions (dimerization, hydrogen abstraction, and addition to ethylene) for representative organic diradicals and diradicaloids in their two lowest spin states. Differences and similarities in reactivity of diradicals vs monoradicals, based on either a localized or delocalized view, whichever is suitable, are then discussed. The last part of this review begins with an extensive, comparative, and critical survey of available measures of diradical character and ends with an analysis of the consequences of diradical character for selected diradicaloids.

Original languageEnglish (US)
Pages (from-to)11291-11351
Number of pages61
JournalChemical Reviews
Volume119
Issue number21
DOIs
StatePublished - Nov 13 2019

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Dimerization
Interchanges
Molecular orbitals
Ground state
Electronic structure
Hydrogen
Activation energy
Molecules
Electrons
ethylene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Stuyver, T., Chen, B., Zeng, T., Geerlings, P., De Proft, F., & Hoffmann, R. (2019). Do Diradicals Behave like Radicals? Chemical Reviews, 119(21), 11291-11351. https://doi.org/10.1021/acs.chemrev.9b00260
Stuyver, Thijs ; Chen, Bo ; Zeng, Tao ; Geerlings, Paul ; De Proft, Frank ; Hoffmann, Roald. / Do Diradicals Behave like Radicals?. In: Chemical Reviews. 2019 ; Vol. 119, No. 21. pp. 11291-11351.
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Stuyver, T, Chen, B, Zeng, T, Geerlings, P, De Proft, F & Hoffmann, R 2019, 'Do Diradicals Behave like Radicals?', Chemical Reviews, vol. 119, no. 21, pp. 11291-11351. https://doi.org/10.1021/acs.chemrev.9b00260

Do Diradicals Behave like Radicals? / Stuyver, Thijs; Chen, Bo; Zeng, Tao; Geerlings, Paul; De Proft, Frank; Hoffmann, Roald.

In: Chemical Reviews, Vol. 119, No. 21, 13.11.2019, p. 11291-11351.

Research output: Contribution to journalReview article

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Stuyver T, Chen B, Zeng T, Geerlings P, De Proft F, Hoffmann R. Do Diradicals Behave like Radicals? Chemical Reviews. 2019 Nov 13;119(21):11291-11351. https://doi.org/10.1021/acs.chemrev.9b00260