Platinum photoredox catalysts for trifluoromethylation
Cyclometalated Pt(II) complexes trifluoromethylate unactivated alkenes in >82% yield under 450 nm LEDs by oxidatively quenching CF3I.
Source
Mechanisms and applications of cyclometalated Pt(ii) complexes in photoredox catalytic trifluoromethylation
Study at a glance
- Design
- Other — Blue-LED photoredox trifluoromethylation catalyzed by cyclometalated Pt(II) complexes
- N
- Synthetic photoredox catalysis — no sample N
- Population
- Alkenes and heteroarenes under Pt(II)/CF3I photoredox conditions
- Outcome
- Trifluoromethylation yields and oxidative-quenching mechanism
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Inspect source passages
Platinum photoredox catalysts for trifluoromethylation
These passages occur verbatim in the stored paper text. They support the points listed below; they do not verify every statement in the explanation.
Isolated yields of trifluoromethylated alkenes exceeded 82%.
The isolated yields of the trifluoromethylated alkenes exceeded 82%, whereas moderate yields were obtained from the trifluoromethylation of heteroarenes.
Photoirradiation used blue LEDs at 450 nm and 7 W.
The reaction mixture was photoirradiated using blue LEDs (450 nm, 7 W) at room temperature, and the progress of the reaction was monitored using gas chromatography or thin-layer chromatography.
What they did
Authors irradiated alkenes and heteroarenes with 1 mol% Pt(II), CF3I, and an amine base under blue LEDs, then measured photoluminescence quenching and compared yields with Ru and Ir photoredox standards.
What they found
Alkene products exceed 82% isolated yield; 1-dodecene finishes in 6 h and N-methylpyrrole in 30 h. No product without Pt or light. Catalysis proceeds by oxidative quenching; catalyst regeneration by sacrificial donor is likely rate-limiting, with >1.43 eV driving force from the substrate radical.
The limits
What it doesn't show
Heteroarene yields are only moderate; the paper does not invent a new CF3 reagent or run a process photochemistry scale-up.
Key terms
- Photoredox catalysis
- Visible-light excitation of a metal complex that transfers an electron to start a radical reaction.
- Oxidative quenching
- Excited catalyst donates an electron to CF3I, becoming Pt(III).
- 3MLCT
- Long-lived triplet metal-to-ligand charge-transfer state after intersystem crossing.
- CF3I
- Iodotrifluoromethane source of ·CF3 after reductive C–I cleavage.
- Back electron transfer
- Wasteful return of the electron before ·CF3 escapes the cage.
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Quiz yourself
Alkene CF3 products isolated in:
Common questions
What light and loading?
450 nm blue LEDs, 1.0 mol% Pt.
Alkene yields?
Isolated yields exceeded 82%.
Which quenching path?
Oxidative quenching only, due to high excited-state potentials.
What limits the cycle?
Regeneration by the sacrificial donor, not ·CF3 generation.
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