In Silico Screening of P,N-Ligands Facilitates Optimization of Au(III)-Mediated S-Arylation

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In silico examination of 13 P , N -ligated Au( iii ) OACs determined the key mechanistic factors governing )-mediated S -arylation. Three complexes were synthesized which exhibited bimolecular coordination rate constants as high 20 200 M −1 s .

Язык: Английский

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Furfural-bridged silsesquioxane-based hybrid network rich in heteroatoms for selective adsorption and reduction of Au(III) in the aqueous phase

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 159826 - 159826

Опубликована: Янв. 1, 2025

Язык: Английский

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Insertion of Molecular Oxygen into a Gold(III)–Hydride Bond

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 4045 - 4059

Опубликована: Янв. 30, 2024

The use of molecular oxygen as an oxidant in chemical synthesis has significant environmental and economic benefits, it is widely used such large-scale industrial processes. However, its adoption highly selective homogeneous catalytic transformations, particularly to produce oxygenated organics, been hindered by our limited understanding the mechanisms which O2 reacts with transition metals. Of particular relevance are reactions late metal hydrides these centers better poised release products. Homogeneous catalysis gold complexes markedly increased, herein we report full characterization a rare AuIII–H, supported diphosphine pincer ligand (tBuPCP = 2,6-bis(di-tert-butylphosphinomethyl)benzene). [(tBuPCP)AuIII–H]+ was found cleanly react yield stable AuIII–OOH complex that also fully characterized. Extensive kinetic studies on reaction via variable temperature NMR spectroscopy have completed, results consistent autoaccelerating radical chain mechanism. observed behavior exhibits similarities previously reported PdII–H PtIV–H but not any known insertion As such, this study contributes nascent fundamental aerobic oxidation hydrides.

Язык: Английский

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Lewis Acid-Assisted C(sp³)–C(sp³) Reductive Elimination at Gold

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(19), С. 10800 - 10808

Опубликована: Май 3, 2023

The phosphine-borane iPr2P(o-C6H4)BFxyl2 (Fxyl = 3,5-(F3C)2C6H3) 1-Fxyl was found to promote the reductive elimination of ethane from [AuMe2(μ-Cl)]2. Nuclear magnetic resonance monitoring revealed intermediate formation (1-Fxyl)AuMe2Cl complex. Density functional theory calculations identified a zwitterionic path as lowest energy profile, with an overall activation barrier more than 10 kcal/mol lower without borane assistance. Lewis acid moiety first abstracts chloride generate Au(III) complex, which then readily undergoes C(sp3)-C(sp3) coupling. is finally transferred back boron gold. electronic features this Lewis-assisted at gold have been deciphered by intrinsic bond orbital analyses. Sufficient acidity required for ambiphilic ligand trigger coupling, shown complementary studies two other phosphine-boranes, and addition chlorides slows down ethane.

Язык: Английский

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Nanoporous gold-catalyzed borylation of C(sp3)–O bonds in dialkyl ethers and its mechanistic elucidation

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Selective cleavage and functionalization of C–O bonds in ethers is a longstanding challenge organic synthesis due to their inherent stability. This particularly significant for synthesizing alkylboron compounds, which serve as versatile intermediates diverse transformations. However, the high chemical stability dialkyl makes successful borylation rare. Herein, we present heterogeneous catalytic various with B₂pin₂ using an unsupported nanoporous gold catalyst (AuNPore). The nanosized, sponge-like operates without need metal oxide supports or bases, efficiently converting wide range acyclic cyclic ethers, well acetals, into alkyl monoboronates diboronates. Mechanistic studies indicate that AuNPore promotes B–B bond cleavage, leading deoxygenative carbocation formation. enables unprecedented pathway via formation C(sp³)–Au–Bpin organogold species, undergoes reductive elimination yield products.

Язык: Английский

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Chelating-Group-Assisted C(sp²)–O Reductive Elimination at the Gold(III) Center

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

Herein, we demonstrate chelating-group-assisted C(sp2)-O reductive elimination at gold(III) centers. Detailed stoichiometric studies highlighted the importance of a chelating group for achieving successful C-O elimination, paving way development catalytic version. The mechanistic investigations, including control experiments, 31P NMR, mass spectrometry, and density functional theory (DFT) studies, suggested that synergistic effect ligand creates highly coordinated environment around Au(III) center to facilitate bond-forming reaction.

Язык: Английский

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Comparative Study of Pd-Mediated Carbon–Carbon, Carbon–Heteroatom, and Heteroatom–Heteroatom Bond Formation/Breakage (C ═ C_sp³, C_sp², C_sp; X = B, N, O, Si, P, S, Se, Te)

Organometallics, Год журнала: 2023, Номер 43(1), С. 1 - 13

Опубликована: Дек. 23, 2023

Carbon–carbon and carbon–heteroatom bond formations via direct reductive elimination as one of the possible mechanisms in Pd(II) complexes are key stages catalytic processes fine organic synthesis. For (R)2Pd(L)2, (X)2Pd(L)2 (R)(X)Pd(L)2 (where R = Me, Vin, Ph, or Eth; X B, N, O, Si, P, S, Se, Te; L PPh3), R–R, R–X, X–X formation barriers reaction energies were calculated. The for C–C C–X coupling decrease series Csp3 > Csp Csp2. activity groups containing a heteroatom decreases heteroatoms Se ≫ N O (for Csp2 types carbon centers) P type center). relationship between structural lability (R)2Pd(L)2 probability was determined by DFT molecular dynamics. An analysis calculated energy showed that, most cases, their values unsymmetrical RX intermediate reactions symmetrical RR XX coupling. influence electronic properties on stabilization cis form complexes, which suitable pre-reaction elimination, shown. additivity difference trans isomers established: cis–trans isomerization corresponding complexes. A high degree QTAIM charge palladium atom all considered analyzed. In present detailed study, we establish hierarchy barriers, emphasizing center types, discern impact heteroatoms, revealing distinct trends based types.

Язык: Английский

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The Role of Inverted Ligand Field in the Electronic Structure and Reactivity of Octahedral Formal Platinum (IV) Complexes**

Chemistry - A European Journal, Год журнала: 2023, Номер 29(59)

Опубликована: Июль 31, 2023

Platinum complexes are ubiquitous in chemistry and largely used as catalysts or precursors drug chemistry, thus a deep knowledge of their electronic properties may help planning new synthetic strategies exploring potential applications. Herein, the structure many octahedral platinum is drastically revised especially when they feature electronegative elements such halogens chalcogens. The investigation revealed that most cases five d orbitals invariably full, empty antibonding orbitals, usually localized on metal, mainly centered ligands, suggesting questionable assignment formal oxidation state IV. analysis supports occurrence inverted ligand field theory all with only exceptions Pt-F Pt-O bonding. trends for molecular mirrored also by density states plots extended structures featuring moieties association chalcogens atoms. Finally, oxidative addition Se-Cl linkage to square complex achieve an moiety has been framework field.

Язык: Английский

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Halogen addition to NHC-gold(I) chloride complexes in the framework of the Inverted Ligand Field

Inorganica Chimica Acta, Год журнала: 2023, Номер 560, С. 121810 - 121810

Опубликована: Окт. 13, 2023

The conversion of LAuX to LAuX3, where L is a neutral ligand such as phosphane or carbene and X = Cl, Br I, can be performed by halogen addition reactions in mild conditions. formation complexes with mixed halides, LAuY2X, also evoking the possibility geometrical isomerization, less investigated. In this work iodine bromine reactions, under conditions, symmetrically disubstituted 1,3-dimethyl-imidazolyl-2-yl-gold(I)chloride were considered. molecular structures highlight trans LAuI2Cl case mixture isomers for bromine. DFT analysis points out stepwise atom linear gold(I) complex without net change metal electronic population, suggesting occurrence Inverted Ligand Field.

Язык: Английский

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Gold Catalyzed Fluorination of Alkynes/Allenes; Mechanistic Explanations and Reactions Scope

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Since the beginning of this century, there has been a great deal research on homogeneous gold-catalyzed alkyne fluorination due to precious values fluorinated scaffolds in many bioactive natural products, drugs, and agrochemicals. This area research, which originally took advantage gold's mild Lewis acidity tendency form π-complexes with alkynes, gained new momentum after Sadighi's discovery 2007 Au-catalyzed hydrofluorination internal alkynes. The methods have enabled direct access valuable fluoroalkanes, fluoroalkenes, α-fluorocarbonyls, carbo- hetero-cycles one pot from readily available precursors. Both nucleophilic electrophilic modes versatile reactivity used achieve several cascade reactions. study covers literature reports published since provides comprehensive summary methods, applications, mechanistic insights into using fluorinating reagents.

Язык: Английский

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