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A Luminescent Zirconium(IV) Complex as a Molecular Photosensitizer for Visible Light Photoredox Catalysis
Abstract
Titanium and zirconium complexes carrying two 2,6-bis(pyrrolyl)pyridine ligands have been synthesized and characterized. The neutral complexes Ti( Me PDP) 2 and Zr( Me PDP) 2 ( Me PDP = 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine) show intense ligand-to-metal charge-transfer bands in the visible region and undergo multiple reversible redox events under highly reducing conditions. Zr( Me PDP) 2 exhibits photoluminescent behavior and its excited state can be quenched by mild reductants to generate a powerful electron transfer reagent with a ground state potential of −2.16 V vs Fc +/0 . This reactivity was utilized to facilitate dehalogenation reactions, the reduction of electron-poor olefins, and the reductive coupling of benzyl bromide via photoredox catalysis. In these reactions, the earth-abundant metal complex Zr( Me PDP) 2 acts as a substitute for the precious metal photosensitizer [Ru(bpy) 3 ] 2+ .
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Cites
Prier, C. K., Rankic, D. A., & MacMillan, D. W. C. (2013) · Chemical Reviews · doi:10.1021/cr300503r · Cited by 9,590
Cited by
Lee, L. C.-C., & Lo, K. K.-W. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c03437 · Cited by 279
Metadata
- Authors
- Zhang, Y., Petersen, J. L., & Milsmann, C.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2016-09-27
- Volume
- 138
- Issue
- 40
- Pages
- 13115-13118
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2522704194
- Cited by
- 191
- References
- 1
- FWCI
- 6.68
- Type
- journal article
- Language
- en
- Open access
- closed
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- Zhang, Y., Petersen, J. L., & Milsmann, C. (2016). A Luminescent Zirconium(IV) Complex as a Molecular Photosensitizer for Visible Light Photoredox Catalysis. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.6b05934
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