3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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Visible‐Light‐Induced Organic Photochemical Reactions through Energy‐Transfer Pathways

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(6), С. 1586 - 1604

Опубликована: Май 18, 2018

Abstract Visible‐light photocatalysis is a rapidly developing and powerful strategy to initiate organic transformations, as it closely adheres the tenants of green sustainable chemistry. Generally, most visible‐light‐induced photochemical reactions occur through single‐electron transfer (SET) pathways. Recently, energy‐transfer (EnT) have received considerable attentions from synthetic community this provides distinct reaction pathway, remarkable achievements been made in field. In Review, we highlight recent advances EnT reactions.

Язык: Английский

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Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(12), С. 5461 - 5476

Опубликована: Март 5, 2020

The association of an electron-rich substrate with electron-accepting molecule can generate a new molecular aggregate in the ground state, called electron donor-acceptor (EDA) complex. Even when two precursors do not absorb visible light, resulting EDA complex often does. In 1952, Mulliken proposed quantum-mechanical theory to rationalize formation such colored complexes. However, and besides few pioneering studies 20th century, it is only past years that photochemistry has been recognized as powerful strategy for expanding potential visible-light-driven radical synthetic chemistry. Here, we explain why this photochemical approach was overlooked so long. We critically discuss historical context, scientific reasons, serendipitous observations, landmark discoveries were essential progress field. also outline future directions identify key advances are needed fully exploit photochemistry.

Язык: Английский

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Heterogeneous Single-Atom Photocatalysts: Fundamentals and Applications

Chemical Reviews, Год журнала: 2020, Номер 120(21), С. 12175 - 12216

Опубликована: Март 18, 2020

Single-atom photocatalysts have shown their compelling potential and arguably become the most active research direction in photocatalysis due to fascinating strengths enhancing light-harvesting, charge transfer dynamics, surface reactions of a photocatalytic system. While numerous comprehensions about single-atom recently been amassed, advanced characterization techniques vital theoretical studies are strengthening our understanding on these materials, allowing us forecast working mechanisms applications photocatalysis. In this review, we begin by describing general background definition photocatalysts. A brief discussion metal-support interactions is then provided. Thereafter, current available for summarized. After having some fundamental photocatalysts, advantages discussed. Finally, end review with look into remaining challenges future perspectives We anticipate that will provide inspiration discovery manifestly stimulating development emerging area.

Язык: Английский

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Mechanistic Studies in Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(12), С. 3730 - 3747

Опубликована: Окт. 19, 2018

Abstract The fast‐moving fields of photoredox and photocatalysis have recently provided fresh opportunities to expand the potential synthetic organic chemistry. Advances in light‐mediated processes mainly been guided so far by empirical findings quest for reaction invention. general perception, however, is that entering a more mature phase where combination experimental mechanistic studies will play dominant role sustaining further innovation. This Review outlines key consider when developing photochemical process, best techniques available acquiring relevant information. discussion use selected case highlight how investigations can be instrumental guiding invention development synthetically useful photocatalytic transformations.

Язык: Английский

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Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts

Chemical Reviews, Год журнала: 2021, Номер 121(21), С. 13051 - 13085

Опубликована: Авг. 11, 2021

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as sole energy input. Following this dual-functional photocatalytic strategy, dreamlike pathway for constructing C–C/C–X (X = C, N, O, S) bonds from abundant readily available X–H bond-containing compounds concomitant release of fulfilled without need external chemical reagents, thus offering green fascinating synthetic strategy. In review, we begin by presenting concise overview on general background traditional production then focus fundamental principles cooperative coupling selective simultaneous utilization photoexcited electrons holes over semiconductor-based catalysts to meet economic sustainability goal. Thereafter, put dedicated emphasis recent key progress various transformations, including alcohol oxidation, methane conversion, amines coupling, cross-coupling, cyclic alkanes dehydrogenation, reforming lignocellulosic biomass, so on. Finally, remaining challenges future perspectives flourishing area have been critically discussed. It anticipated that review will provide enlightening guidance rational design such system, thereby stimulating development economical environmentally benign solar generation value-added fine chemicals.

Язык: Английский

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A Toolbox Approach To Construct Broadly Applicable Metal-Free Catalysts for Photoredox Chemistry: Deliberate Tuning of Redox Potentials and Importance of Halogens in Donor–Acceptor Cyanoarenes

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(45), С. 15353 - 15365

Опубликована: Окт. 2, 2018

The targeted choice of specific photocatalysts has been shown to play a critical role for the successful realization challenging photoredox catalytic transformations. Herein, we demonstrate implementation rational design strategy series deliberate structural manipulations cyanoarene-based, purely organic donor-acceptor photocatalysts, using 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as starting point. Systematic modifications both donor substituents well acceptors' molecular core allowed us identify strongly oxidizing reducing catalysts (e.g., an unprecedented detriflation unactivated naphthol triflate), which additionally offer remarkably balanced redox potentials with predictable trends. Especially halogen arene substitutions are instrumental our alterations catalysts' properties. Based on their preeminent electrochemical and photophysical characteristics, all novel, were evaluated in three challenging, mechanistically distinct classes benchmark reactions (either requiring balanced, highly or properties) enormous potential customizable that outperform complement prevailing typical best photocatalysts.

Язык: Английский

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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Год журнала: 2021, Номер 7(3), С. 415 - 431

Опубликована: Март 9, 2021

Efficient and selective molecular syntheses are paramount to

Язык: Английский

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Copper’s rapid ascent in visible-light photoredox catalysis

Science, Год журнала: 2019, Номер 364(6439)

Опубликована: Май 2, 2019

Visible-light photoredox catalysis offers a distinct activation mode complementary to thermal transition metal catalyzed reactions. The vast majority of processes capitalizes on precious ruthenium(II) or iridium(III) complexes that serve as single-electron reductants oxidants in their photoexcited states. As low-cost alternative, organic dyes are also frequently used but general suffer from lower photostability. Copper-based photocatalysts rapidly emerging, offering not only economic and ecological advantages otherwise inaccessible inner-sphere mechanisms, which have been successfully applied challenging transformations. Moreover, the combination conventional with copper(I) copper(II) salts has emerged an efficient dual catalytic system for cross-coupling

Язык: Английский

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Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1543 - 1625

Опубликована: Окт. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Язык: Английский

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