Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza-Hetero Aromatic Compounds

Calogero F, Wilczek L, Pinosa E, Gualandi A, Dorta R, Herrera A, Dai Y, Rossignol A, Negri F, Ziani Z, Fermi A, Ceroni P, Cozzi PG (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 63

Article Number: e202411074

Journal Issue: 44

DOI: 10.1002/anie.202411074

Abstract

Excited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short-lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long-lived excited state, was identified as the competent species for the reduction of challenging organic substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox<−3 V vs. SCE in their excited states, determined by DFT and time-dependent TD-DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron-rich aryl chlorides and to form C−C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Authors with CRIS profile

Romano Dorta Professur für Anorganische Chemie Alberto Cesar Herrera Professur für Anorganische Chemie

Involved external institutions

University of Bologna / Università di Bologna IT Italy (IT)

How to cite

APA:

Calogero, F., Wilczek, L., Pinosa, E., Gualandi, A., Dorta, R., Herrera, A.,... Cozzi, P.G. (2024). Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza-Hetero Aromatic Compounds. Angewandte Chemie International Edition, 63(44). https://doi.org/10.1002/anie.202411074

MLA:

Calogero, Francesco, et al. "Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza-Hetero Aromatic Compounds." Angewandte Chemie International Edition 63.44 (2024).

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