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Exploring Norrish type I and type II reactions: an ab initio mechanistic study highlighting singlet-state mediated chemistry

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)14418-14428
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume21
Early online date5 Feb 2019
DOIs
DateAccepted/In press - 5 Feb 2019
DateE-pub ahead of print - 5 Feb 2019
DatePublished (current) - 5 Jul 2019

Abstract

Norrish reactions are important photo-induced reactions in mainstream organic chemistry and are implicated in many industrially and biologically relevant processes and in the processing of carbonyl molecules in the atmosphere. The present study reports multi-reference electronic structure calculations designed to assess details of the potential energy profiles associated with the Norrish type-I and type-II reactions of a prototypical ketone 5-methyl-hexan-2-one. We show that the well-established ‘triplet state mediated’ reaction pathways following initial population of a singlet excited state can be complemented by (hitherto rarely recognized) ‘singlet state only’ Norrish type-I and type-II reaction mechanisms that involve no spin-forbidden transitions along the respective reaction paths, and suggest how the efficiencies of such reactions might be affected by strategic substitutions at selected sites within the parent ketone.

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  • Full-text PDF (accepted author manuscript)

    Rights statement: This is the accepted author manuscript (AAM). The final published version (version of record) is available online via The Royal Society of Chemistry at https://doi.org/10.1039/C8CP07292B . Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 793 KB, PDF document

    Embargo ends: 5/02/20

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  • Full-text PDF Supplementary Material

    Rights statement: This is the accepted author manuscript (AAM). The final published version (version of record) is available online via The Royal Society of Chemistry at https://doi.org/10.1039/C8CP07292B . Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 1 MB, PDF document

    Embargo ends: 5/02/20

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    Licence: Other

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