期刊
CHEMICAL SCIENCE
卷 13, 期 32, 页码 9165-9175出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2sc02122f
关键词
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资金
- Swedish Foundation for Strategic Research (SSF) [EM16-0067]
- Knut and Alice Wallenberg (KAW) [2018.0074]
- Swedish Research Council (VR) [2020-03207, 2020-05058]
- Swedish Energy Agency (Energimyndigheten)
- LMK Foundation
- Sten K Johnson Foundation
- Wenner-Gren Sti.elserna
- Swedish Research Council [2020-05058, 2020-03207] Funding Source: Swedish Research Council
- Swedish Foundation for Strategic Research (SSF) [EM16-0067] Funding Source: Swedish Foundation for Strategic Research (SSF)
Fe-N-heterocyclic carbene (NHC) complexes have been studied for their application in visible light-mediated atom transfer radical addition. Utilizing [Fe(iii)(btz)(3)](3+) with long excited state lifetimes in both oxidation states, efficient one-electron reduction of alkyl halides was achieved under green light irradiation.
Fe-N-heterocyclic carbene (NHC) complexes attract increasing attention as photosensitisers and photoredox catalysts. Such applications generally rely on sufficiently long excited state lifetimes and efficient bimolecular quenching, which leads to there being few examples of successful usage of Fe-NHC complexes to date. Here, we have employed [Fe(iii)(btz)(3)](3+) (btz = (3,3 '-dimethyl-1,1 '-bis(p-tolyl)-4,4 '-bis(1,2,3-triazol-5-ylidene))) in the addition of alkyl halides to alkenes and alkynes via visible light-mediated atom transfer radical addition (ATRA). Unlike other Fe-NHC complexes, [Fe(iii/ii)(btz)(3)](3+/2+) benefits from sizable charge transfer excited state lifetimes >= 0.1 ns in both oxidation states, and the Fe(iii) (LMCT)-L-2 and Fe(ii) (MLCT)-M-3 states are strong oxidants and reductants, respectively. The combined reactivity of both excited states enables efficient one-electron reduction of the alkyl halide substrate under green light irradiation. The two-photon mechanism proceeds via reductive quenching of the Fe(iii) (LMCT)-L-2 state by a sacrificial electron donor and subsequent excitation of the Fe(ii) product to its highly reducing (MLCT)-M-3 state. This route is shown to be more efficient than the alternative, where oxidative quenching of the less reducing Fe(iii) (LMCT)-L-2 state by the alkyl halide drives the reaction, in the absence of a sacrificial electron donor.
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