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Photoredox Catalysis Mediated by Tungsten(0) Arylisocyanides in 1,2-Difluorobenzene

Barth, Alexandra T. and Morales, Maryann and Winkler, Jay R. and Gray, Harry B. (2022) Photoredox Catalysis Mediated by Tungsten(0) Arylisocyanides in 1,2-Difluorobenzene. Inorganic Chemistry, 61 (19). pp. 7251-7255. ISSN 0020-1669. doi:10.1021/acs.inorgchem.1c03767.

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We have studied the photochemical cyclization of 1-(2-iodobenzyl)-pyrrole (IBP) and 1-(2-bromobenzyl)-pyrrole (BBP) to 5H-pyrrolo[2,1-a]isoindol catalyzed by W(CNDipp)₆ (CNDipp = 2,6-diisopropylphenylisocyanide) in 1,2-difluorobenzene (DFB). Irradiation (445 nm) of W(CNDipp)₆ (5 mol %) in DFB solution converted 78% of IBP (50 mM) to product after 1 h (16 turnovers). Addition of tetra-n-butyl ammonium hexafluorophosphate (TBAPF₆) (0.2 M) to the DFB solution led to rapid photoinduced disappearance of W(CNDipp)₆ but, remarkably, did not inhibit photochemical cyclization of IBP, indicating that IBP cyclization could be driven by a nonluminescent photocatalyst.

Item Type:Article
Related URLs:
URLURL TypeDescription
Barth, Alexandra T.0000-0002-1813-4029
Morales, Maryann0000-0002-1778-8901
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2022 American Chemical Society. Received 3 December 2021. Published online 29 April 2022. Published in issue 16 May 2022. We thank Javier Fajardo, Jr. for helpful discussions. We thank the National Science Foundation (Grant CHE-1763429) and the Caltech Beckman Institute Laser Resource Center supported by the Arnold and Mabel Beckman Foundation. A.T.B. acknowledges a National Science Foundation Graduate Research Fellowship (NSF Grant No. DGE-1745301). Author Contributions. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest.
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
NSF Graduate Research FellowshipDGE-1745301
Subject Keywords:Aromatic compounds, Catalysts, Cyclization, Irradiation, Solvents
Issue or Number:19
Record Number:CaltechAUTHORS:20220520-231863000
Persistent URL:
Official Citation:Photoredox Catalysis Mediated by Tungsten(0) Arylisocyanides in 1,2-Difluorobenzene Alexandra T. Barth, Maryann Morales, Jay R. Winkler, and Harry B. Gray Inorganic Chemistry 2022 61 (19), 7251-7255 DOI: 10.1021/acs.inorgchem.1c03767
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114870
Deposited By: George Porter
Deposited On:24 May 2022 14:39
Last Modified:24 May 2022 14:39

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