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. https://resolver.caltech.edu/CaltechAUTHORS:20220520-231863000

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Abstract

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:

URL	URL Type	Description
https://doi.org/10.1021/acs.inorgchem.1c03767	DOI	Article

ORCID:

Author	ORCID
Barth, Alexandra T.	0000-0002-1813-4029
Morales, Maryann	0000-0002-1778-8901
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.

Funders:

Funding Agency	Grant Number
NSF	CHE-1763429
Arnold and Mabel Beckman Foundation	UNSPECIFIED
NSF Graduate Research Fellowship	DGE-1745301

Subject Keywords:

Aromatic compounds, Catalysts, Cyclization, Irradiation, Solvents

Issue or Number:

DOI:

10.1021/acs.inorgchem.1c03767

Record Number:

CaltechAUTHORS:20220520-231863000

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20220520-231863000

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

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ID Code:

114870

Collection:

CaltechAUTHORS

Deposited By:

George Porter

Deposited On:

24 May 2022 14:39

Last Modified:

24 May 2022 14:39

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