C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex

Lim, Jia Hui; Engelmann, Xenia; Corby, Sacha; Ganguly, Rakesh; Ray, Kallol; Soo, Han Sen

doi:10.1039/c7sc05378a

Cited by 15 publications

(9 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Earth abundant substitutes, Cu‐ and Fe‐based sensitizers, are already known. Many research groups share the aspiration to create more sustainable versions of photocatalysts, and extensive work is conducted on synthesis and application of earth‐abundant substitutes – copper iron, nickel, vanadium complexes, just to name a few.…”

Section: Introductionmentioning

confidence: 99%

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Savateev

Antonietti

2019

ChemCatChem

View full text Add to dashboard Cite

Molecular photoredox complexes from the platinum group paved the way of organic photocatalysis. However, high price and difficulties related to removal and recycling hamper application of such complexes on the larger scale. Carbon nitride semiconductor photocatalysts are deprived at large extent of such limitations. Herein, we summarize application of ionic carbon nitrides in photocatalysis. A salt-like structure of ionic carbon nitrides comprising negatively charged poly (heptazine imide) anion and positively charged alkali metal cations gives rise to a number of unique properties and high activity in photocatalysis. The performance of ionic carbon nitrides in H 2 generation is up to 100 times higher compared with the covalent graphitic carbon nitrides. Eleven photocatalytic reactions mediated by ionic carbon nitrides and their long-lived radicals are reviewed. Economy of using carbon nitride photocatalysts in comparison with the photoredox complexes from the platinum group has been analyzed.

show abstract

Section: Introductionmentioning

confidence: 99%

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Savateev

Antonietti

2019

ChemCatChem

View full text Add to dashboard Cite

show abstract

“…For instance, Choi and coworkers investigated the oxidation of the more toxic As III to As V with a TiO 2 photoanode under both aerobic and anaerobic conditions, with the former being irreversible owing to the more efficient scavenging of conduction band electrons by O 2 . We proposed using a molecular co‐catalyst well known for the efficient mineralization of recalcitrant pollutants, (TAML)Fe V (O) complexes, in a photochemical cycle as part of a PEC for artificial photosynthesis (Figure ) . (TAML)Fe III complexes were pioneered by Collins and his team over several decades and could be activated and oxidized by H 2 O 2 to the Fe V (O) form to fully degrade pollutants such as pentachlorophenol .…”

Section: Pecs For Pollutant Degradationmentioning

confidence: 99%

“…(TAML)Fe III complexes were pioneered by Collins and his team over several decades and could be activated and oxidized by H 2 O 2 to the Fe V (O) form to fully degrade pollutants such as pentachlorophenol . We sought to harness the potent activity of (TAML)Fe V (O) complexes and attempted to use molecular photosensitizers such as Ru(bpy) 3 to photochemically oxidize the precursor . We identified that a potential pitfall could be nucleophilic attack on the unprotected aromatic rings by ions in solution and are now working toward new variants that can be co‐catalysts when deposited on photoanodes in a PEC.…”

Section: Pecs For Pollutant Degradationmentioning

confidence: 99%

“…We sought to harness the potent activity of (TAML)Fe V (O) complexes and attempted to use molecular photosensitizers such as Ru(bpy) 3 to photochemically oxidize the precursor . We identified that a potential pitfall could be nucleophilic attack on the unprotected aromatic rings by ions in solution and are now working toward new variants that can be co‐catalysts when deposited on photoanodes in a PEC. We believe that a greater variety of pollutant substrates and photocatalytic materials should be considered in future PECs to achieve both artificial photosynthesis and environmental remediation together.…”

Section: Pecs For Pollutant Degradationmentioning

confidence: 99%

See 1 more Smart Citation

Photoelectrochemical Cells for Artificial Photosynthesis: Alternatives to Water Oxidation

Boruah

Chin

et al. 2020

ChemNanoMat

Self Cite

View full text Add to dashboard Cite

Photoelectrochemical cells have been used as one of the most common artificial photosynthetic approaches to mimic natural photosynthetic water splitting reactions. However, despite the tremendous advances made to improve the affordability and efficiency of photoelectrochemical water splitting, it is still not an economically feasible method to produce solar fuels currently since only the H 2 evolving reduction half-reaction generates valuable fuels. Therefore, in this review, we intend to highlight other underexplored substrates and reactions for producing solar fuels in photo-electrochemical cells, as well as alternative architectures including temporally independent and biohybrid systems. We show that besides water oxidation, electrocatalytic or photoredox reactions for pollutant degradation, biomass valorization, and organic chemical synthesis can be or have been successfully adapted for photoelectrochemical cells, thus offering a virtually infinite number of possibilities for artificial photosynthetic applications which generate valuable products in both the reduction and oxidation half reactions.

show abstract

“…Against this backdrop, our group has been actively pursuing photoredox catalytic processes that can generate value‐added organic precursors or degrade pollutants, and can eventually be integrated into AP systems (Figure B). Notably, we developed vanadium(V) photocatalysts ( 2a–2f , Figure S1, Supporting Information) that can selectively cleave the activated CC bond adjacent to the benzylic alcohol in lignin model substrates ( Figure ) .…”

Section: Introductionmentioning

confidence: 99%

Visible Light–Driven Cascade Carbon–Carbon Bond Scission for Organic Transformations and Plastics Recycling

et al. 2019

Self Cite

View full text Add to dashboard Cite

Significant efforts are devoted to developing artificial photosynthetic systems to produce fuels and chemicals in order to cope with the exacerbating energy and environmental crises in the world now. Nonetheless, the large-scale reactions that are the focus of the artificial photosynthesis community, such as water splitting, are thus far not economically viable, owing to the existing, cheaper alternatives to the gaseous hydrogen and oxygen products. As a potential substitute for water oxidation, here, a unique, visible light-driven oxygenation of carboncarbon bonds for the selective transformation of 32 unactivated alcohols, mediated by a vanadium photocatalyst under ambient, atmospheric conditions is presented. Furthermore, since the initial alcohol products remain as substrates, an unprecedented photodriven cascade carboncarbon bond cleavage of macromolecules can be performed. Accordingly, hydroxyl-terminated polymers such as polyethylene glycol, its block co-polymer with polycaprolactone, and even the non-biodegradable polyethylene can be repurposed into fuels and chemical feedstocks, such as formic acid and methyl formate. Thus, a distinctive approach is presented to integrate the benefits of photoredox catalysis into environmental remediation and artificial photosynthesis.

show abstract

C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex

Abstract: The (photo) chemical oxidation of a (TAML)FeIII complex using outer-sphere oxidants results in valence tautomerisation and C–H activation governed by exogenous anions.

Cited by 15 publications

References 50 publications

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Photoelectrochemical Cells for Artificial Photosynthesis: Alternatives to Water Oxidation

Visible Light–Driven Cascade Carbon–Carbon Bond Scission for Organic Transformations and Plastics Recycling

Contact Info

Product

Resources

About