Integrating proton coupled electron transfer (PCET) and excited states

Gagliardi, Christopher J.; Westlake, Brittany C.; Kent, Caleb A.; Paul, Jared J.; Papanikolas, John M.; Meyer, Thomas J.

doi:10.1016/j.ccr.2010.03.001

Cited by 170 publications

(223 citation statements)

References 48 publications

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“…They offer the advantages of rapid iteration by chemical synthesis and the ability to study individual components separately. Contemporary interest in chemical approaches to artificial photosynthesis is apparent by the large number of reviews that have appeared in recent years (25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38).…”

Section: Methodsmentioning

confidence: 99%

Chemical approaches to artificial photosynthesis

Concepcion

House

Papanikolas

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Section: Methodsmentioning

confidence: 99%

Chemical approaches to artificial photosynthesis

Concepcion

House

Papanikolas

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

384

322

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“…In a particularly dramatic example from Photosystem II, electron transfer between a Tyr Z /His190 pair (Y z ) and P680 + proceeds with a forward rate constant ~ 10 7 s −1 , with back-electron transfer between P680 + and Q A •− proceeding at ~10 3 s −1 [144]. In the forward reaction, Meyer has noted that the necessity of His190 in water oxidation [145][146][147] provides strong evidence for the necessity of proton movement in oxidation of Yz [144]. Sluggish back electron transfer can be attributed to the both long distance involved (17-18 Å) as well as the high driving force (−1.4 eV); the thermodynamic favorability causes back electron transfer to occur in the Marcus-inverted region and the distance of electron transfer further slows this charge recombination process.…”

Section: Phenolsmentioning

confidence: 99%

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

Miller

Tarantino

Knowles

2016

Topics in Current Chemistry Collections

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Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter we aim to highlight the origins, development and evolution of PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups.

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“…1e, 3 Unfortunately, multielectron and proton reactions are kinetically unfavorable, and as such, to compromise between high-energy input and multiple electron transfers, catalysts are required. To achieve multielectron redox reactions, metal complexes are ideal candidates 4 with metal centers that have variable oxidation states, and interchangeable ligands that can facilitate the reduction of specific molecules, such as CO 2 .…”

Section: ■ Introductionmentioning

confidence: 99%

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

et al. 2013

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The reduction of CO 2 in a biphasic liquid-condensed gas system was investigated as a function of the CO 2 pressure. Using 1-benzyl-1,4-dihydronicotinamide (BNAH) as sacrificial electron donor dissolved in a dimethylformamide−water mixture and [Ru(bpy) 2 (CO)L]n+ as a catalyst and [Ru(bpy) 3 ]2+ as a photosensitizer, the reaction was found to produce a mixture of CO and formate, in total about 250 μmol after just 2 h. As CO 2 pressure increases, CO formation is greatly favored, being four times greater than that of formate in aqueous systems. In contrast, formate production was independent of CO 2 pressure, present at about 50 μmol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO 2 concentration favored the CO catalytic cycle. Under optimum conditions, a turnover number (TON) of 125 was obtained. Further investigations of the component limits led to an unprecedented TON of over 1000, and an initial turnover frequency (TOF) of 1600 h −1.

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Integrating proton coupled electron transfer (PCET) and excited states

Cited by 170 publications

References 48 publications

Chemical approaches to artificial photosynthesis

Chemical approaches to artificial photosynthesis

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

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Integrating proton coupled electron transfer (PCET) and excited states

Cited by 170 publications

References 48 publications

Chemical approaches to artificial photosynthesis

Chemical approaches to artificial photosynthesis

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

Photoreduction of CO2 Using [Ru(bpy)2(CO)L]n+ Catalysts in Biphasic Solution/Supercritical CO2 Systems

Contact Info

Product

Resources

About

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems