Abstract Electrocatalytic water oxidation using the oxidatively robust 2,7‐[bis(2‐pyridylmethyl)aminomethyl]‐1,8‐naphthyridine ligand (BPMAN)‐based dinuclear copper(II) complex, [Cu 2 (BPMAN)(μ‐OH)] 3+ , has been investigated. This catalyst exhibits high reactivity and stability towards in neutral aqueous solutions. DFT calculations suggest that OO bond formation takes place by an intramolecular direct coupling mechanism rather than a nucleophilic attack of on high‐oxidation‐state Cu IV O moiety.

We report systematic quantum mechanics‐only (QM‐only) and QM/molecular mechanics (MM) calculations on an enzyme‐catalyzed reaction to assess the convergence behavior of QM‐only QM/MM energies with respect size chosen QM region. The MM parts are described by density functional theory (typically B3LYP/def2‐SVP) CHARMM force field, respectively. Extending our previous work acetylene hydratase regions up 157 atoms (Liao Thiel, J. Chem. Theory Comput. 2012, 8, 3793), we performed geometry...

Solar-powered water splitting is a dream reaction for constructing an artificial photosynthetic system producing solar fuels. Natural photosystem II prototype template research on energy conversion by oxidizing into molecular oxygen and supplying four electrons fuel production. Although range of synthetic oxidation catalysts have been developed, the understanding O-O bond formation in this multielectron multiproton catalytic process limited, thus still big challenge. Herein, we report...

Direct CAr-F arylation is effective and sustainable for synthesis of polyfluorobiaryls with different degrees fluorination, which are important motifs in medical material chemistry. However, no aid transition metals, the engagement bond activation has proved difficult. Herein, an unprecedented transition-metal-free strategy reported site-selective polyfluoroarenes simple (het)arenes. By merging N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide)-catalyzed electrophotocatalytic...

Parent amido complexes are crucial intermediates in ammonia-based transformations. We report a well-defined ferric ammine system [Cp*Fe(1,2-Ph2PC6H4NH)(NH3)]+ ([1-NH3]+), which processes electrocatalytic ammonia oxidation to N2 and H2 at mild potential. Through establishing elementary e-/H+ conversions with the ammine, formal Fe(IV)-amido species, [1-NH2]+, together its conjugated Lewis acid, [1-NH3]2+, was isolated structurally characterized for first time. Mechanism studies indicated that...

The design and production of active, durable, nonprecious electrocatalysts toward alkaline hydrogen oxidation evolution reactions (HOR/HER) are extremely appealing for the implementation economy, but remain challenging. Here, we report a facile electric shock synthesis an efficient, stable, inexpensive NiCoCuMoW multi-element alloy on Ni foam (NiCoCuMoW) as bifunctional electrocatalyst both HOR HER. For HOR, current density could reach ∼11.2 mA cm

Abstract Reported here is the first catalytic atroposelective electrophilic amination of indoles, which delivers functionalized atropochiral N ‐sulfonyl‐3‐arylaminoindoles with excellent optical purity. This reaction was furnished by 1,6‐nucleophilic addition to p ‐quinone diimines. Control experiments suggest an ionic mechanism that differs from radical pathway commonly proposed for 1,6‐addition quinones. The origin selectivity investigated through computational studies. Preliminary studies...

The development of chiral ligands to fine-tune the stereocontrol has been recognized as a crucial pillar asymmetric catalysis. In contrast well-developed pyridine–pyridine-type and pyridine–oxazoline-type ligands, oxazole–pyridine-type have rarely exploited. this study, class [2.2]paracyclophane-based planar-chiral oxazole–pyridine N,N-ligands designed synthesized. These presented superior performance in enantioselective palladium-catalyzed acetoxylative cyclization alkyne-tethered...

The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such transformation with high efficiency. A cobalt-centered N,N-bidentate complex was designed employed as metal–ligand cooperative catalyst. Detailed kinetic studies, control experiments, DFT calculations revealed the crucial hydride transfer, proton evolution processes....

Abstract Small molecules with conformationally rigid, three-dimensional geometry are highly desirable in drug development, toward which a direct, simple-to-complexity synthetic logic is still of considerable challenges. Here, we report intermolecular aza-[2 + 2] photocycloaddition (the aza-Paternò–Büchi reaction) indole that facilely assembles planar building blocks into ladder-shape azetidine-fused indoline pentacycles contiguous quaternary carbons, divergent head-to-head/head-to-tail...

Acetylene hydratase is a tungsten-dependent enzyme that catalyzes the nonredox hydration of acetylene to acetaldehyde. Density functional theory calculations are used elucidate reaction mechanism this with large model active site devised on basis native X-ray crystal structure. Based calculations, we propose new in which substrate first displaces W-coordinated water molecule, and then undergoes nucleophilic attack by molecule assisted an ionized Asp13 residue at site. This followed proton...

We report a comparison of QM-only and QM/MM approaches for the modeling enzymatic reactions. For this purpose, we present case study on formation vinyl alcohol in catalytic cycle tungsten-dependent acetylene hydratase. Three different QM regions ranging from 32 to 157 atoms are designed reinvestigation previously suggested one-water attack mechanism. The calculations with minimal region M1 (32 atoms) yield two-step reaction profile, an initial nucleophilic followed by protonation formed...

Biofouling can be overcome with zwitterion grafts and antimicrobial, metallic nanoparticles. However, the mechanism underpinning this effective approach remains unclear. To elucidate role of each component in system while maximizing membrane antifouling antimicrobial properties, here we performed a comparative study to investigate impact type their interactions Ag various states. Two different zwitterions (SO3–-based COO–-based) were employed modify polyamide (PA) thin film composite (TFC)...

During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting H2O into O2 solar fuels, such as H2. However, bottleneck in artificial photosynthetic schemes oxidation half reaction where more efficient catalysts are required that lower kinetic barrier for this process. In particular based on earth-abundant metals highly attractive compared to comprised noble metals. We have...

Catalytic hydrogenation or transfer of quinolines was thought to be a direct strategy access dihydroquinolines. However, the challenge is control chemoselectivity and regioselectivity. Here we report an efficient partial system operated by cobalt-amido cooperative catalyst, which converts 1,2-dihydroquinolines reaction with H

An air-stable half-sandwich nickel(II) complex bearing a phosphinophenolato ligand, Cp*Ni(1,2-Ph2PC6H4O) (1), has been designed and synthesized for activation of HBpin catalytic hydroboration N-heteroarenes such as pyridine. Through addition the H–B bond across Ni–O bond, 1 reacts with to afford an 18-electron Ni(II)–H intermediate [H1(Bpin)] featuring oxygen-stabilized boron moiety, which readily reduces pyridine analogues give 1,2-hydroborated product, thus accomplishing cycle under mild...

Abstract Herein, we report the importance of structure regulation on O−O bond formation process in binuclear iron catalysts. Three complexes, [Fe 2 (μ‐O)(OH ) (TPA) ] 4+ ( 1 ), (6‐HPA)] and (BPMAN)] 3 have been designed as electrocatalysts for water oxidation 0.1 M NaHCO solution (pH 8.4). We found that are molecular catalysts proceeds via oxo–oxo coupling rather than by nucleophilic attack (WNA) pathway. In contrast, complex displays negligible catalytic activity. DFT calculations suggested...

Density functional theory (DFT) calculations have been conducted to investigate the mechanism of cobalt(II) tetraamino phthalocyanine (CoPc-NH2) catalyzed electro-reduction CO2. Computational results show that catalytically active species 1 (4[CoII(H4L)]0) is formed by a four-electron-four-proton reduction initial catalyst CoPc-NH2. Complex can attack CO2 after one-electron give [CoIII-CO22-]- intermediate, followed protonation and intermediate [CoII-COOH]- (4). 4 then protonated on its...

Abstract In this study, we highlight the impact of catalyst geometry on formation O−O bonds in Cu 2 and Fe catalysts. A series complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, catalytic performance these is enhanced their molecular skeletons become more rigid, which contrasts behavior observed our previous investigation analogs. Moreover, mechanistic studies reveal that reactivity bridging O atom results distinct pathways bond systems,...

We present a systematic study of the decarboxylation step enzyme aspartate decarboxylase with purpose assessing quantum chemical cluster approach for modeling this important class enzymes. Active site models ranging in size from 27 to 220 atoms are designed, and barrier reaction energy evaluated. To model surrounding, homogeneous polarizable medium techniques used several dielectric constants. The main conclusion is that when active reaches certain size, solvation effects surroundings...

Abstract Density functional calculations are used to elucidate the reaction mechanism of water oxidation catalyzed by iron tetraamido macrocyclic ligand (TAML) complexes. The starting TAML–Fe 3+ –OH 2 complex removing three electrons and two protons leads formation a key intermediate, TAML · –Fe 5+ =O, which can undergo nucleophilic attack either molecule or nitrate ion. Both pathways involve on oxo group lead production O . is more favoured has total barrier 15.4 kcal/mol. alternative...

DFT calculations are used to elucidate the reaction mechanism, role of chlorosilyl group, and primary <italic>vs.</italic> secondary C(sp³)–H C(sp²)–H selectivity iridium-catalyzed borylation chlorosilanes.