Ein bidentates Antimon‐Pniktogenbrücken‐Wirtsystem DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Sept. 29, 2023

Abstract Ein zweizähniges Pniktogenbrücken‐Wirtsystem auf der Basis von 1,8‐Diethinylanthracen wurde mittels einer selektiven Zinn‐Antimon‐Austauschreaktion hergestellt und seine Fähigkeit untersucht, als Lewis‐saure Wirtskomponente für die Komplexierung Lewis‐basischen oder anionischen Gästen zu fungieren. In dieser Arbeit mit C≡C−Sb(C 2 F 5 ) ‐Gruppe eine neuartige Akzeptorfunktion etabliert, das Potenzial Antimon(III)‐Funktionen Vertreter kaum erforschten Pniktogenbrücken‐Donatoren untersucht werden kann. Die Akzeptorfähigkeit dieses teilfluorierten Wirtsystems gegenüber Halogenidanionen (Cl − , Br I ), Dimethylchalkogeniden Me Y (Y = O, S, Se, Te) Stickstoffheterozyklen (Pyridin, Pyrimidin) untersucht. Einblicke in Adduktbildungsverhalten sowie Bindungssituation solcher E⋅⋅⋅Sb−C ‐Einheiten wurden Lösung NMR‐Spektroskopie, im festen Zustand durch Röntgenbeugung, Elementaranalysen rechnerische Methoden (DFT, QTAIM, IQA) gewonnen.

The Matere Bond DOI Creative Commons
Rosa M. Gomila, Antonio Frontera

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This article explores matere bonds, supported by theoretical and computational studies. These σ-hole interactions with group 7 elements (Mn, Tc, Re) are key in crystal engineering, catalysis, biological systems.

Language: Английский

Citations

4
Control of Selectivity in Homogeneous Catalysis through Noncovalent Interactions DOI Creative Commons
Kamran T. Mahmudov⧫, Armando J. L. Pombeiro

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(26)

Published: Feb. 23, 2023

The regio-, site-, stereo- or chemoselective homogeneous catalytic transformations are extremely important for the growth/success of current chemical industry. Based on empirical, theoretical intuitive knowledge, several synthetic strategies, such as ligand design, transient directing group, metal node alternation, metal-ligand cooperation, pore decoration, biomimetic, have already been developed selective functionalization organic substrates. In comparison to other tactics, use noncovalent interactions control selectivity in compounds may avoid multi-steps, reduce time procedure, decrease cost operation, and increase reactivity catalyst. fact, enzymes achieve a high through biochemical processes Nature. Guided by impressive performance biosynthesis biodegradation reactions, various types complex organocatalysts developed, which catalyst-substrate pivotal impact distinctive stabilization transition states intermediates, improving efficiency reactions. Herein, we highlight recent relevant examples directing/driving function transformation substrate(s) catalyzed both catalysts.

Language: Английский

Citations

31
A Bidentate Antimony Pnictogen Bonding Host System DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

Abstract A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as Lewis acidic host component for the complexation of basic or anionic guests. In this work, novel C≡C−Sb(C 2 F 5 ) unit established study potential antimony(III) sites representatives scarcely explored donors. The capability partly fluorinated system towards halide anions (Cl − , Br I ), dimethyl chalcogenides Me Y (Y=O, S, Se, Te), nitrogen heterocycles (pyridine, pyrimidine). Insights into adduct formation behavior well situation such E⋅⋅⋅Sb−C moieties were obtained in solution means NMR spectroscopy, solid state X‐ray diffraction, elemental analyses, computational methods (DFT, QTAIM, IQA), respectively.

Language: Английский

Citations

21
The Origin of Anion−π Autocatalysis DOI Creative Commons
M. Ángeles Gutiérrez López, Mei‐Ling Tan, Antonio Frontera

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 3(4), P. 1039 - 1051

Published: March 17, 2023

The autocatalysis of epoxide-opening ether cyclizations on the aromatic surface anion−π catalysts stands out as a leading example emergent properties expected from integration unorthodox interactions into catalysis. A working hypothesis was proposed early on, but mechanism has never been elucidated. Here, we show that is almost independent peripheral crowding in substrate and product. Inaccessible asymmetric sometimes erratic reproducibility further support origin more complex than originally assumed. apparent long-distance communication without physical contact calls for inclusion water between product catalytic surface. Efficient around equimolar amounts poor activity dry solvents with excess indicate this requires high precision. Computational models suggest two molecules transmit dual activation by serve proton shuttles along antiparallel decoupled hydrogen-bonded chains to delocalize stabilize evolving charge density transition state "anion−π double bonds". This new transition-state model provides plausible explains experimental results brings catalysis an unprecedented level sophistication.

Language: Английский

Citations

15
Cross‐Electrophile C−PIIICoupling of Chlorophosphines with Organic Halides: Photoinduced PIIIand Aminoalkyl Radical Generation Enabled by Pnictogen Bonding DOI

Yongliang Tu,

Bei‐Bei Zhang,

Bingsheng Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(43)

Published: Sept. 5, 2023

Pnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, development of a straightforward much simpler protocol cross-electrophile C-PIII coupling remains ongoing challenge with organic halides. In this study, we present simple photoinduced PnB-enabled couplings using readily available chlorophosphines halides via merging single electron transfer (SET) halogen atom (XAT) processes. photomediated transformation, PnB formed between alkyl amines facilitates photogeneration PIII radicals α-aminoalkyl through SET. Subsequently, resulting activate C-X bonds XAT, leading to formation carbon radicals. This methodology offers operational simplicity compatibility both aliphatic aromatic

Language: Английский

Citations

14
Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices DOI Creative Commons
M. Ángeles Gutiérrez López, Rojan Ali, Mei‐Ling Tan

et al.

Science Advances, Journal Year: 2023, Volume and Issue: 9(41)

Published: Oct. 12, 2023

The vision to control the charges migrating during reactions with external electric fields is attractive because of promise general catalysis, emergent properties, and programmable devices. Here, we explore this idea anion-π that stabilization anionic transition states on aromatic surfaces. Catalyst activation by polarization system most effective. This induced fields. use electrochemical microfluidic reactors polarize multiwalled carbon nanotubes as catalysts emerges essential. These provide access high at low enough voltage prevent electron transfer, afford meaningful effective catalyst/substrate ratios, avoid interference from additional electrolytes. Under these conditions, rate pyrene-interfaced epoxide-opening ether cyclizations linearly voltage-dependent positive voltages negligible negative voltages. While electromicrofluidics have been conceived for redox chemistry, our results indicate their supramolecular organocatalysis has potential noncovalently electrify organic synthesis in broadest sense.

Language: Английский

Citations

12
A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems DOI Creative Commons
Giacomo Renno, Qingxia Zhang, Antonio Frontera

et al.

Helvetica Chimica Acta, Journal Year: 2024, Volume and Issue: 107(5)

Published: March 6, 2024

Abstract It is often said that pnictogen‐bonding catalysis, and σ ‐hole catalysis in general, would not work aqueous systems because the solvent interfere as an overcompetitive pnictogen‐bond acceptor. In this study, we show transfer of from hydrophobic solvents to possible by replacing only with hydrophilic substrates, without changing catalyst or reaction. This differs conventional covalent Lewis acid catalysts, which are instantaneously destroyed ligand exchange. With their water‐proof substituents place exchangeable ligands, supramolecular counterpart evinced catalyze hydrogenation quinolines neutral systems. To secure these results, introduce a water‐soluble fluorogenic substrate releases coumarin upon reduction instead activated quinolidiniums, stiborane catalysts deepened holes. They demonstrate can operate higher‐order architectures for under biologically relevant conditions, provide operational assay high‐throughput screening fluorescence imaging, situ conditions.

Language: Английский

Citations

4
Pnictogen‐Bonding Enzymes DOI Creative Commons
Giacomo Renno, Dongping Chen, Qingxia Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 5, 2024

Abstract The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a σ‐hole interaction is essentially absent in biocatalysis. For purpose, stibine catalysts were equipped with biotin derivative and combined streptavidin mutants identify an efficient transfer hydrogenation catalyst for the reduction fluorogenic quinoline substrate. Increased catalytic activity from wild‐type best coincides depth σ hole Sb(V) center, emergence saturation kinetic behavior. Michaelis–Menten analysis reveals transition‐state recognition low micromolar range, more than three orders magnitude stronger millimolar substrate recognition. Carboxylates preferred by contribute hydrogen‐bonded ion pairing anion‐π interactions emerging pyridinium product. challenging stereoselectivity aqueous systems further emphasizes compatibility bonding higher order catalysis.

Language: Английский

Citations

4
Poly-pnictogen bonding: trapping halide ions by a tetradentate antimony(iii) Lewis acid DOI Creative Commons
J. Louis Beckmann, Jonas Krieft, Yury V. Vishnevskiy

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13551 - 13559

Published: Jan. 1, 2023

A tetradentate host system with four CC–Sb(C 2 F 5 ) functions binds halide ions in a distorted square planar coordination. Experimental and calculated structures reveal complex interplay of attractive pnictogen bonding Coulomb repulsion.

Language: Английский

Citations

9
Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis DOI

Yongliang Tu,

Xiangyu Chen, Xiang Li

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

Abstract N-Heterocyclic nitreniums (NHNs) are isoelectronic and isostructural analogues of N-heterocyclic carbenes (NHCs). Unlike NHCs, NHNs much less developed. While a comprehensive understanding NHN reactivity remains elusive, recent advancements have demonstrated their utility as Lewis acid catalysts, photoreductants, photooxidants, leading to several reaction patterns. In this short review, we focus on the applications in photoredox reactions. We also discuss mechanisms behind these transformations outline future research directions. 1 Introduction 2 Application Nitreniums Photoreductants 3 Facilitate Photohomolysis 4 Photooxidants 5 Conclusion

Language: Английский

Citations

3