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Strongly reducing Ir photoredox on aryl chlorides
Ir(ppy)2(NacNac) photocatalysts with BIH hydrodehalogenate unactivated aryl bromides, chlorides, fluorides, and alkyl bromides, including with green light.
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What ancillary ligand makes these Ir photocatalysts extra reducing?
A β-diketiminate (NacNac) in Ir(ppy)2(NacNac).
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
How much more reducing is the excited state versus fac-Ir(ppy)3?
About 300–500 mV.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
What are E(IrIV/*IrIII) for Ir1 and Ir2?
−2.6 V and −2.4 V versus ferrocene.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Which sacrificial reductant is used?
BIH (1,3-dimethyl-2-phenylbenzimidazoline).
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
What loading/time does BIH enable?
1 mol% Ir and 24 h, versus 2.5 mol%/48 h with TMEDA.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Can aryl chlorides be hydrodechlorinated?
Yes; Ir1/blue LEDs give quantitative yields on four substrates.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Does green light work?
Ir2 under 520–525 nm LEDs gives comparable yields on most substrates.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
What quantum yields were measured?
4.7% (S2) and 1.4% (S7).
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Do reactions continue in the dark?
No; conversion stops when the light is off.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Besides hydrodehalogenation, what else works?
Radical cyclization, arylation, prenylation, ketone reduction, and ether C–O cleavage.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified
Are aryl fluorides in scope?
Yes; they also demonstrate hydrodefluorination and prenylation of S13.
Source: Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers · DOI · quote verified