Ligand electronic fine-tuning and its repercussion on the photocatalytic activity and mechanistic pathways of the copper-photocatalysed aza-Henry Reaction
MetadataShow full item record
A family of six structurally related heteroleptic copper(I) complexes of the form of [Cu(N^N)(P^P)]+ bearing a 2,9-dimethyl-1,10-phenanthroline diimine (N^N) ligand and a series of electronically tunable xantphos (P^P) ligands have been synthesized and their optoelectronic properties characterized. The reactivity of these complexes in the copper-photocatalyzed Aza-Henry reaction of N-Phenyltetrahydroisoquinoline was evaluated, while the related excited state kinetics were comprehensively studied. By subtlety changing the electron-donating properties of the P^P ligands with neglegible structural differences, we could tailor the photoredox properties and relate it to their reactivity. Moreover, depending on the exited-state redox potential of the catalysts, the preferred mechanism can shift between reductive quenching, energy transfer and oxidative quenching pathways. A combined study of structural modulation of copper(I) photocatalysts, optoelectronic properties and photocatalytic reactivity resulted in a clearer understanding of both the rational design of the photocatalyst and the complexity of competing photoinduced electron and energy transfer mechanisms.
Li , C , Dickson , R , Rockstroh , N , Rabeah , J , Cordes , D B , Slawin , A M Z , Hünemörder , P , Spannenberg , A , Buehl , M , Mejía , E , Zysman-Colman , E & Kamer , P C J 2020 , ' Ligand electronic fine-tuning and its repercussion on the photocatalytic activity and mechanistic pathways of the copper-photocatalysed aza-Henry Reaction ' , Catalysis Science & Technology , vol. Advance Article . https://doi.org/10.1039/D0CY01221A
Catalysis Science & Technology
Copyright © 2020 the Author(s). This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
DescriptionC.Li thanks the Prof. & Mrs Purdie Bequests Scholarship and AstraZeneca PhD Studentship.
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.