Issue 26, 2019

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

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
27 နို 2018
Accepted
05 ဖေ 2019
First published
05 ဖေ 2019

Phys. Chem. Chem. Phys., 2019,21, 14418-14428

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

B. Marchetti, T. N. V. Karsili and M. N. R. Ashfold, Phys. Chem. Chem. Phys., 2019, 21, 14418 DOI: 10.1039/C8CP07292B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements