The electrocatalytic activity of transition-metal-based compounds is strongly related to the spin states. However, underlying relationship connecting catalytic remains unclear. Herein, we carried out density functional theory calculations on oxygen reduction reaction (ORR) catalyzed by Fe single-atom supported C2N (C2N–Fe) shed light this relationship. It found that change electronic moments and O2 due molecular-catalyst adsorption scales with amount electron transfer from O2, which promotes...

We present herein a high yield, highly selective catalytic synthesis of vinylboronate esters (VBEs), including 1,1-disubstituted VBEs, from alkenes without significant hydrogenation or hydroboration, using the simple catalyst precursor, trans-[RhCl(CO)(PPh3)2] (1), and diboron reagents B2pin2 (2a, pin = pinacolato OCMe2CMe2O) B2neop2 (2b, neop neopentylglycolato OCH2CMe2CH2O), monoboron reagent HBpin, all which are commercially available. The reactions were conducted at 80 degrees C...

A Pd- and norbornene-catalyzed domino procedure has been developed to synthesize indoline compounds.

Microneedles, which are used in minimally invasive transdermal drug delivery, have tremendous application potential the fields of biosensing, disease diagnosis, bioelectrical signal detection, and wound management. Although manufacturing methods for microneedles technically well-established, continuously evolving scientific clinical applications require more intricate bespoke microneedle structures that cannot be fabricated using conventional techniques. Three-dimensional (3D) printing is an...

The global prevalence of diabetes mellitus is experiencing a notable increase. Diabetic patients need to consistently monitor their fluctuating glucose levels caused by the changing diet. Meanwhile, with face higher risk developing oral ulcer than healthy individuals. Fortunately, three-dimensional (3D)-printed food, which design- and texture-customizable, presents potential solution alleviate discomfort while providing personalized nutrition for unique dietary requirements. In this study,...

The reaction mechanisms on the NHC-catalyzed [4 + 3] and 1] annulations of enals with azoalkenes have been theoretically investigated aid density functional theory calculations. It is found that additives play an important role in promoting proton transfer dehydration. impacts catalysts (NHC-A NHC-B) substituent groups regioselectivity were rationalized. origin involved these reactions was probed by performing distortion-interaction analysis. For A NHC-A as catalyst Boc group substituent,...

Treatment of [RuHCl(CO)(PPh3)3] with CH2CCMe2 produced the new allyl complex [Ru(η3-CH2CHCMe2)Cl(CO)(PPh3)2], which slowly isomerizes to [Ru(η3-CH2CMeCHMe)Cl(CO)(PPh3)2] in both solution and solid state. While endo exo isomers can be observed by NMR for only isomer was detected other related analogous complexes [Ru(η3-allyl)Cl(CO)(PPh3)2] (e.g. = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated computational chemistry. theoretical calculations show that metal−η3-allyl...

The reaction mechanisms for the MTO-catalyzed deoxygenation of epoxides and diols were investigated with aid density functional theory (DFT) calculations. DFT results indicate that starts a [2σ+2π] addition epoxide to MTO give five-membered-ring rhena-2,5-dioxolane intermediate, followed by H2 addition, proton transfer, extrusion olefin regenerate catalyst. experimental observation formation subsequent disappearance diol appearing in catalytic is explained as follows. Diol was produced...

A density functional theory study was performed to understand the detailed mechanisms of cross-benzoin reactions catalyzed by N-heterocyclic carbene (NHC) species.

The Au(<sc>i</sc>)-catalyzed cycloisomerization reactions of 1,6-enylnyl ester are theoretically investigated to rationalize the observed product divergences by modulating H₂O participation.

Density functional theory (DFT) calculations have been performed to unravel the mechanism of Lewis-acid-induced Ni(cod)2-catalyzed selective coupling reactions one diketene and two alkynes. Complex mixtures (unsymmetrical phenylacetic acid P1, symmetrical P2 (3E)-4-ethyl-5-methylene-3-heptenoic P3) were obtained in absence Et2Al(OEt). P1 formation involves C(sp2)-O oxidative addition diketene, twice alkyne insertion, intramolecular C═C acidolysis, β-H elimination. For P2/P3 formation, common...

High crystallinity porous MgO microrods were synthesized <italic>via</italic> a NaCl and NP-9 assisted calcination of the hydrothermally MgC₂O₄·2H₂O microrods, which exhibited satisfactory removal efficiency for Pb(<sc>ii</sc>) Cr(<sc>vi</sc>) ions from aqueous solutions.

Gold-catalyzed cyclization of 2-alkynyl-N-propargylanilines provides a step-economic method for the construction three-dimensional indolines. In this article, M06 functional density theory was employed to gain deeper insights into reaction mechanism and associated intriguing experimental observations. The found first undergo Au(I)-induced form an indole intermediate, 1,3-propargyl migration, substitution with substrate 2-alkynyl-N-propargylaniline (R1) generate intermediate product P1,...

The detailed mechanism of the Pd(0)-catalyzed cross-coupling aryl iodide, benzoic anhydride and ethyl acrylate was clarified by theoretical methods.

The mechanisms and chemo- regioselectivities of divergent (Ni(cod)2/PCy3)-mediated/-catalyzed C(sp3)–F bond activation 2-trifluoromethyl-1-alkenes (1) with alkynes (2) were investigated by density functional theory (DFT) calculations. nickel-mediated/-catalyzed reaction involves sequential ligand exchange, alkene coordination, oxidative cyclization (1 + Ni(0) 2), first β-F(C(sp3)) elimination to give a common requisite alkenylnickel(II) species, which bifurcates into either stoichiometric...

DFT calculations are performed to understand the conjugated N–N bond cleavage by Rh(<sc>iii</sc>)-catalyzed redox-neutral C–H activation of pyrazolones with PhCCPh.

Cu-catalyzed aerobic C(CO)–CH3 activation of (hetero)aryl methyl ketones provides a rare tool for aldehyde formation from through oxidative processes. To elucidate the detailed reaction mechanism, combined computational and experimental study was performed. Computational indicates dinuclear spin-crossover-involved mechanism explains formation. Meanwhile, α-mono(hydroxy)acetophenone int1 found to be real active intermediate benzaldehyde pro1 acetophenone sub1. sub1 transforms into via oxygen...

We discovered a cooperative gold/silver catalysis mechanism in the oxidative cross-coupling reaction between 1,2,4,5-tetrafluorobenzene and N-TIPS-indole, using DFT calculations. A silver(I)-catalyzed CMD is responsible for C-H activation of 1,2,4,5-tetrafluorobenzene, acidity determines chemoselectivity. gold(III)-catalyzed SE2Ar C3-H arene nucleophilicity chemo- regioselectivity. The orthogonal chemoselectivity control provides mechanistic guide dual reactions.

The mechanism of ruthenium-catalyzed [4 + 1] annulation benzamide and propargyl alcohol has been investigated by density functional theory calculations. reaction undergoes N–H C–H deprotonations a concerted metalation-deprotonation to afford 5-membered ruthenacyclic species, which then ring expansion alkyne insertion deliver 7-membered intermediate. Our study focused on how the successive hydrogen migrations take place that remains unclear. 1,2-proton migration 1,3-proton transfer from O C...

Gem-hydrogenative cycloisomerization and sigmatropic rearrangement reactions of propargyl alcohol derivatives with different Ru(II) catalysts afforded cyclopropanation, cyclopentenylation, cyclohexenylation, enol acetate, respectively. To understand the mechanism origin product selectivity, density functional theory calculations were performed. Calculated results reveal that electron-abundant neutral active catalyst [Cp*RuCl] facilitate formation a Cl- counterion-assisted π-back bonding...

Density functional theory calculations at the B3LYP level have been performed to investigate mechanism of zirconocene-catalyzed addition ortho C−H bond α-picoline propene produce 2-Me-6-iPr-pyridine. The computational results support proposed mechanism, which involves (i) 2-Me-pyridine dissociation from [Cp2Zr(2-Me-6-pyridyl)(2-Me-pyridine)]+ followed by insertion into Zr−C η2-pyridyl complex Cp2Zr(η2-2-Me-6-pyridyl)+ (1) yield azametallacycle Cp2Zr{η2-C,N-CH2CHMe-(2-Me-6-pyridyl)}+ (2),...

By carrying out density functional theory calculations, we have performed a detailed mechanism study for the cycloisomerization reaction of 4-phenyl-hexa-1,5-enyne catalyzed by homogeneous gold to better understand observed different catalytic activity several catalysts, including (PPh3)AuBF4, (PPh3)AuCl, AuCl3, and AuCl. In all situations, is found involve two major steps: initial nucleophilic addition alkynyl onto alkene group subsequent 1,2-H migration. It that potential energy surface...