Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2021 Sep 20;60(39):21100-21115.
doi: 10.1002/anie.202100270. Epub 2021 Jun 18.

Visible-Light-Induced Homolysis of Earth-Abundant Metal-Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis

Youssef Abderrazak  1 , Aditya Bhattacharyya  1 , Oliver Reiser  1
Affiliations
Review

Visible-Light-Induced Homolysis of Earth-Abundant Metal-Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis

Youssef Abderrazak et al. Angew Chem Int Ed Engl. .

Abstract

The mainstream applications of visible-light photoredox catalysis predominately involve outer-sphere single-electron transfer (SET) or energy transfer (EnT) processes of precious metal RuII or IrIII complexes or of organic dyes with low photostability. Earth-abundant metal-based Mn Ln -type (M=metal, Ln =polydentate ligands) complexes are rapidly evolving as alternative photocatalysts as they offer not only economic and ecological advantages but also access to the complementary inner-sphere mechanistic modes, thereby transcending their inherent limitations of ultrashort excited-state lifetimes for use as effective photocatalysts. The generic process, termed visible-light-induced homolysis (VLIH), entails the formation of suitable light-absorbing ligated metal-substrate complexes (Mn Ln -Z; Z=substrate) that can undergo homolytic cleavage to generate Mn-1 Ln and Z. for further transformations.

Keywords: 3d transition metals; dissociative ligand-to-metal charge transfer; inner-sphere electron transfer; photoredox catalysis; visible-light-induced homolysis.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Mechanistic features of visible‐light‐induced homolysis (VLIH): Order of the mechanistic events and the modes of photoinduced electronic transitions.
Scheme 1
Scheme 1
Mechanistic features of the VLIH of CuII species and selected transformations.
Scheme 2
Scheme 2
Mechanistic features of the VLIH of nickel species and selected transformations.
Scheme 3
Scheme 3
Mechanistic features of the VLIH of FeIII species and selected transformations.
Scheme 4
Scheme 4
Photo‐ and Co‐acetylide‐catalyzed [2+2+2] cycloaddition reaction.
Scheme 5
Scheme 5
Mechanistic features of the VLIH of CoIII species and selected transformations.
Scheme 6
Scheme 6
Mechanistic features of the VLIH of CeIV species and selected transformations.
Scheme 7
Scheme 7
Recent developments in VLIH: a) Vanadium‐catalyzed oxidative C−C cleavage of lignin and the mechanistic features; b) VLIH in catalysis with a dithiocarbamate anion.
See this image and copyright information in PMC

References

    1. None
    1. Prier C. K., Rankic D. A., MacMillan D. W. C., Chem. Rev. 2013, 113, 5322–5363; - PMC - PubMed
    1. Schultz D. M., Yoon T. P., Science 2014, 343, 1239176; - PMC - PubMed
    1. Marzo L., Pagire S. K., Reiser O., Koenig B., Angew. Chem. Int. Ed. 2018, 57, 10034–10072; - PubMed
    2. Angew. Chem. 2018, 130, 10188–10228;
    1. Shaw M. H., Twilton J., MacMillan D. W. C., J. Org. Chem. 2016, 81, 6898–6926; - PMC - PubMed

LinkOut - more resources