Catalytic cycle
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Hydrogen Atom Transfer (HAT): A Versatile Strategy for Substrate Activation in Photocatalyzed Organic Synthesis Open
The adoption of hydrogen atom transfer (HAT) in a photocatalytic approach, in which an excited catalyst is responsible for substrate activation, offers unique opportunities in organic synthesis, enabling the straightforward activation of R…
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Visible Light-Induced Transition Metal Catalysis Open
In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which has led to the discovery of unprecedented transformations as well as the improvement of known reactions. In th…
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The Road Travelled: After Main‐Group Elements as Transition Metals Open
Since the latter quarter of the twentieth century, main group chemistry has undergone significant advances. Power's timely review in 2010 highlighted the inherent differences between the lighter and heavier main group elements, and that th…
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Oxygen Activation and Energy Conservation by Cytochrome <i>c</i> Oxidase Open
This review focuses on the type A cytochrome c oxidases (C cO), which are found in all mitochondria and also in several aerobic bacteria. C cO catalyzes the respiratory reduction of dioxygen (O2) to water by an intriguing mechanism, the de…
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Merging Visible Light Photoredox Catalysis with Metal Catalyzed C–H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants Open
The development of efficient catalytic systems for direct aromatic C-H bond functionalization is a long-desired goal of chemists, because these protocols provide environmental friendly and waste-reducing alternatives to classical methodolo…
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Mechanisms of Cytochrome P450-Catalyzed Oxidations Open
Enzymes are complex biological catalysts and are critical to life. Most oxidations of chemicals are catalyzed by cytochrome P450 (P450, CYP) enzymes, which generally utilize mixed-function oxidase stoichiometry, utilizing pyridine nucleoti…
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Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO<sub>2</sub> Open
The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic ac…
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Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides Open
The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the…
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A bound reaction intermediate sheds light on the mechanism of nitrogenase Open
Sulfur steps aside for nitrogen Enzymatic conversion of molecular nitrogen to ammonia requires a dance of electrons and protons. The stage for that dance is the nitrogenase cofactor, a carefully constructed cluster of iron, sulfur, and car…
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The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium‐Based Catalysts Open
The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH 3 ) on vanadium‐based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidate…
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Atomistic Insights into Nitrogen-Cycle Electrochemistry: A Combined DFT and Kinetic Monte Carlo Analysis of NO Electrochemical Reduction on Pt(100) Open
Electrocatalytic denitrification is a promising technology for the removal of NOx species in groundwater. However, a lack of understanding of the molecular pathways that control the overpotential and product distribution have limited the d…
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Stereospecific Nickel-Catalyzed Cross-Coupling Reactions of Benzylic Ethers and Esters Open
This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereoch…
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Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne “click reaction” Open
Isolation of bis(copper) complexes that are kinetically more active than their mononuclear counterparts in the most popular “click chemistry” reaction.
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Active sites and mechanisms for H<sub>2</sub>O<sub>2</sub>decomposition over Pd catalysts Open
Significance The use of hydrogen peroxide (H 2 O 2 ) for catalytic oxidations is limited by the energy-intensive and wasteful process by which H 2 O 2 is currently produced—the anthraquinone process. The direct synthesis of H 2 O 2 (DSHP) …
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Insight into G-quadruplex-hemin DNAzyme/RNAzyme: adjacent adenine as the intramolecular species for remarkable enhancement of enzymatic activity Open
G-quadruplex (G4) with stacked G-tetrads structure is able to bind hemin (iron (III)-protoporphyrin IX) to form a unique type of DNAzyme/RNAzyme with peroxidase-mimicking activity, which has been widely employed in multidisciplinary fields…
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Thioetherification via Photoredox/Nickel Dual Catalysis Open
Hypervalent alkylsilicates represent new and readily accessible precursors for the generation of alkyl radicals under photoredox conditions. Alkyl radicals generated from such silicates serve as effective hydrogen atom abstractors from thi…
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Hydrogenative Depolymerization of Nylons Open
The widespread crisis of plastic pollution demands discovery of new and sustainable approaches to degrade robust plastics such as nylons. Using a green and sustainable approach based on hydrogenation, in the presence of a ruthenium pincer …
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Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane Open
A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling betwee…
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A General Organocatalytic System for Electron Donor–Acceptor Complex Photoactivation and Its Use in Radical Processes Open
We report herein a modular class of organic catalysts that, acting as donors, can readily form photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors. Excitation with visible light generates open-shell int…
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Organophotoredox Hydrodefluorination of Trifluoromethylarenes with Translational Applicability to Drug Discovery Open
Molecular editing such as insertion, deletion, and single atom exchange in highly functionalized compounds is an aspirational goal for all chemists. Here, we disclose a photoredox protocol for the replacement of a single fluorine atom with…
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Principles of Dynamic Heterogeneous Catalysis: Surface Resonance and Turnover Frequency Response Open
Acceleration\nof the catalytic transformation of molecules via heterogeneous\nmaterials occurs through design of active binding sites to optimally\nbalance the requirements of all steps in a catalytic cycle. In accordance\nwith the Sabatie…
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Seven Coordinated Molecular Ruthenium–Water Oxidation Catalysts: A Coordination Chemistry Journey Open
Molecular water oxidation catalysis is a field that has experienced an impressive development over the past decade mainly fueled by the promise of generation of a sustainable carbon neutral fuel society, based on water splitting. Most of t…
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Nickel-catalyzed C–N bond activation: activated primary amines as alkylating reagents in reductive cross-coupling Open
The reductive cross coupling of pyridinium salts derived from readily available primary alkyl amines with aryl halides has been achieved under mild reaction conditions using a nickel catalyst.
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Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation Open
Analysis of a promising lignin-first biorefining technique, reductive catalytic fractionation, provides useful metrics for cost and sustainability to guide researchers toward critical areas for improvement.
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Mechanistic Studies of Copper-Catalyzed Asymmetric Hydroboration of Alkenes Open
Mechanistic studies of the copper-catalyzed asymmetric hydroboration of vinylarenes and internal alkenes are reported. Catalytic systems with both DTBM-SEGPHOS and SEGPHOS as the ligands have been investigated. With DTBM-SEGPHOS as the lig…
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Unexpected Hydrated Electron Source for Preparative Visible-Light Driven Photoredox Catalysis Open
The hydrated electron is experiencing a renaissance as a superreductant in lab-scale reductions driven by light, both for the degradation of recalcitrant pollutants and for challenging chemical reactions. However, examples for its sustaina…
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Palladium-Catalyzed C–H Bond Acetoxylation via Electrochemical Oxidation Open
Here we describe the development of a method for the Pd-catalyzed electrochemical acetoxylation of C-H bonds. The oxidation step of the catalytic cycle is probed through cyclic voltammetry and bulk electrolysis studies of a preformed palla…
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Perspectives on Electrostatics and Conformational Motions in Enzyme Catalysis Open
CONSPECTUS: Enzymes are essential for all living organisms, and their effectiveness as chemical catalysts has driven more than a half century of research seeking to understand the enormous rate enhancements they provide. Nevertheless, a co…
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Mechanistic Study of an Improved Ni Precatalyst for Suzuki–Miyaura Reactions of Aryl Sulfamates: Understanding the Role of Ni(I) Species Open
Nickel precatalysts are potentially a more sustainable alternative to traditional palladium precatalysts for the Suzuki-Miyaura coupling reaction. Currently, there is significant interest in Suzuki-Miyaura coupling reactions involving read…
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Catalysis-dependent selenium incorporation and migration in the nitrogenase active site iron-molybdenum cofactor Open
Dinitrogen reduction in the biological nitrogen cycle is catalyzed by nitrogenase, a two-component metalloenzyme. Understanding of the transformation of the inert resting state of the active site FeMo-cofactor into an activated state capab…