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Photochemistry

Eu(II) cryptate photocatalyzes bibenzyl coupling

Jenks TC, Bailey MD, Hovey JL, et al. · Chemical science · 2018

Open access · cc by · source: Europe PMC

A visible-absorbing Eu(II) azacryptate, assembled in situ from EuCl3, ligand and Zn0, reductively couples benzyl chloride to 1,2-diphenylethane with an excited-state potential near −3 V.

Key findings

Stoichiometric irradiation gave 85±2% bibenzyl in 30 min. Catalytic loadings of 5/1/0.5 mol% gave 71/70/60% bibenzyl (~14–120 turnovers). Excited-state E* ≈ −3.0 V vs Ag/AgCl; τ = 0.98 μs; Φ = 37% in MeOH. The system tolerates some water.

Methodology

Authors encapsulated Eu(II) in octaazacryptand 1, measured absorption/emission, lifetime, quantum yield and electrochemistry, then ran blue-light couplings of benzyl chloride with sacrificial Zn0, including wet EuCl3·6H2O conditions.

Limitations

Scope on unactivated aryl bromides is proposed, not demonstrated; E1/2 was measured in DMF not methanol.

How this study connects

Role on claims

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  • SupportsPhotochemistryconcept

    A visible-absorbing Eu(II) azacryptate, assembled in situ from EuCl3, ligand and Zn0, reductively couples benzyl chloride to 1,2-diphenylethane with an excited-state potential near −3 V.

    Evidence for the claim as stated.

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