Issue 23, 2022

Energy transfer (EnT) photocatalysis enabled by gold-N-heterocyclic carbene (NHC) complexes

Abstract

We present the use of gold sensitizers [Au(SIPr)(Cbz)] (PhotAu 1) and [Au(IPr)(Cbz)] (PhotAu 2) as attractive alternatives to state-of-the-art iridium-based systems. These novel photocatalysts are deployed in [2 + 2] cycloadditions of diallyl ethers and N-tosylamides. The reactions proceed in short reaction times and in environmentally friendly solvents. [Au(SIPr)Cbz] and [Au(IPr)(Cbz)] have higher triplet energy (ET) values (66.6 and 66.3 kcal mol−1, respectively) compared to commonly used iridium photosensitizers. These ET values permit the use of these gold complexes as sensitizers enabling energy transfer catalysis involving unprotected indole derivatives, a substrate class previously inaccessible with state-of-the-art Ir photocatalysts. The photosynthesis of unprotected tetracyclic spiroindolines via intramolecular [2 + 2] cycloaddition using our simple mononuclear gold sensitizer is readily achieved. Mechanistic studies support the involvement of triplet–triplet energy transfer (TTEnT) for both [2 + 2] photocycloadditions.

Graphical abstract: Energy transfer (EnT) photocatalysis enabled by gold-N-heterocyclic carbene (NHC) complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Feb 2022
Accepted
18 May 2022
First published
18 May 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 6852-6857

Energy transfer (EnT) photocatalysis enabled by gold-N-heterocyclic carbene (NHC) complexes

E. A. Martynova, V. A. Voloshkin, S. G. Guillet, F. Bru, M. Beliš, K. Van Hecke, C. S. J. Cazin and S. P. Nolan, Chem. Sci., 2022, 13, 6852 DOI: 10.1039/D2SC00864E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements