Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation DOI Creative Commons
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati

et al.

Published: June 28, 2021

Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated pair (FLP) chemistry. While cationic tetrylium acids, being isolobal and iso(valence)electronic, natural replacement boranes, tetrel allude as less trivial options due the absence of formally empty p orbital on acceptor centre. Recently series intramolecular geminal FLPs (C2F5)3E-CH2-P(tBu)2 (E= Si, Ge, Sn) featuring atoms site, were reported for activation small molecules including H2. In this work, through density functional theory computations, we elucidate general mechanistic picture H2 by family FLPs. Our findings reveal that atom derives required acidity utilizing antibonding orbitals its adjacent bonds with individual contributions depending identity donor atoms. By varying acid base attached substituents, unravel their interplay energetics activation. We find switching site from P N significantly affects synchronous nature bond breaking/formations along reaction pathway result, N-bearing have more favourable profile than those P. results quantitatively discussed detail within framework Activation Strain Model reactivity Energy Decomposition Analysis method. Finally, reductive elimination decomposition route pertinent plausible extension catalytic hydrogenation these is also examined

Language: Английский

Alkynyl Sulfonium Salts Can Be Employed as Chalcogen‐Bonding Catalysts and Generate Alkynyl Radicals under Blue‐Light Irradiation DOI
Lu Yu, Qiang Liu, Zhixiang Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(16)

Published: Feb. 4, 2022

Chalcogen bonding (ChB) has emerged as a promising tool in organic synthesis. However, compared with the well-developed selenium- and tellurium-based salt catalysts, ChB catalysis of sulfonium salts is still unknown. Here, we report new type alkynyl-sulfonium for various ionic transformations, including transfer hydrogenation, bromination, bromolactonization, dimerization 1,1-diphenylethylene, nitro-Michael addition reaction Ritter reaction. More importantly, photocapability was first demonstrated to generate alkynyl radicals synthesis variety chalcogenoacetylenes. Mechanistic studies shed light on mechanism photoinduced reactions confirmed involvement which are difficult otherwise.

Language: Английский

Citations

65
A Selenide Catalyst for the Activation of Alkenes through Se⋅⋅⋅π Bonding DOI

Xinglong Yuan,

Yao Wang

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)

Published: April 19, 2022

Chalcogen bonding catalysis with divalent chalcogenides required using heteroatoms as electron donors to give reactivity, while the activation of hydrocarbons such alkenes by this concept remains an unresolved challenge. Herein, we discovered a powerful selenide catalyst that showed unprecedented capability in alkenes. The Se⋅⋅⋅π interactions were capable catalyzing broad range transformations, including intermolecular cyclization and coupling reactions. Significantly, mode can be exploited achieve enyne cyclizations controlled cross-coupling triple selenides opens up new avenue for supramolecular catalysis.

Language: Английский

Citations

25
Frustrated Lewis Pairs Comprising Nitrogen Lewis Acids for Si–H Bond Activation DOI
Idan Avigdori,

Alla Pogoreltsev,

Alexander Kaushanski

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(52), P. 23476 - 23479

Published: Sept. 27, 2020

Abstract N‐heterocyclic nitrogen Lewis acids are a recent addition to the field of organic chemistry. Based on nitrenium cations, these where previously shown generate adducts when combined with appropriate bases. Herein, triazinium‐based acid was t Bu 3 P frustrated pair (FLP) capable cleaving, for first time, Si−H bonds in silanes. Whereas low yields were initially encountered owing insufficient acidity, new nitrenium‐based synthesized, and its superior acidity experimentally computationally confirmed. A FLP based this cleaved bond PhSiH , generating triazane product quantitative yield. This unprecedented N−H fully characterized by multinuclear NMR techniques single‐crystal X‐ray crystallography. class compounds, N‐H triazanes display potential capacity participate hydride transfer reactions.

Language: Английский

Citations

39
Triazenolysis of alkenes as an aza version of ozonolysis DOI
Alexander N. Koronatov, Pavel А. Sakharov, Deepak Ranolia

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 101 - 110

Published: Oct. 11, 2024

Language: Английский

Citations

3
Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species DOI
Etienne A. LaPierre, Lara K. Watanabe, Brian O. Patrick

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9223 - 9232

Published: April 17, 2023

Herein, we report the synthesis of an acyclic carbene-stabilized diphospha(aminyl) PNP radical CAACMePNPCAACMe4 (CAACMe = 1-[2,6-bis(isopropyl)phenyl]-3,3,5,5-tetramethyl-2-pyrrolidinylidene) by a facile one-pot, seven-electron reduction hexachlorophosphazene chloride [Cl3PNPCl3][Cl]. The 4 features conjugated framework with spin density primarily localized on central nitrogen atom as well flanking carbenes. Unlike other tripnictogen radicals, undergoes one-electron oxidation and to yield nonclassical nitrenium amide species [5]+ [6]-, respectively. cation exhibits conformational flexibility in solution state between expected W-shaped geometry [5b]+ previously unobserved linear heteroallene-type structure [5a]+, which was characterized solid state. equilibrium explored both computationally experimentally, showing that [5a]+ is favored over enthalpically (ΔH -2.9 × 103 ± 80 J mol-1) entropically (ΔS 4.2 0.25 mol-1 K-1). formal [6]- displays remarkable its coordination chemistry due presence multiple Lewis basic centers, evidenced potassium complex K262, μ, κ-P, η3-PNP modes. Protonation leads formation amine 7, trigonal planar around nitrogen.

Language: Английский

Citations

7
Alkynyl Sulfonium Salts Can Be Employed as Chalcogen‐Bonding Catalysts and Generate Alkynyl Radicals under Blue‐Light Irradiation DOI
Yu Lu, Qiang Liu, Zhixiang Wang

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(16)

Published: Feb. 4, 2022

Abstract Chalcogen bonding (ChB) has emerged as a promising tool in organic synthesis. However, compared with the well‐developed selenium‐ and tellurium‐based salt catalysts, ChB catalysis of sulfonium salts is still unknown. Here, we report new type alkynyl‐sulfonium for various ionic transformations, including transfer hydrogenation, bromination, bromolactonization, dimerization 1,1‐diphenylethylene, nitro‐Michael addition reaction Ritter reaction. More importantly, photocapability was first demonstrated to generate alkynyl radicals synthesis variety chalcogenoacetylenes. Mechanistic studies shed light on mechanism photoinduced reactions confirmed involvement which are difficult otherwise.

Language: Английский

Citations

11
The Reactivity of Isomeric Nitrenium Lewis Acids with Phosphines, Carbenes, and Phosphide DOI

Diya Zhu,

Zheng‐Wang Qu, Jiliang Zhou

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(8), P. 2861 - 2867

Published: Nov. 2, 2020

Alkylation of spiro[fluorene-9,3'-indazole] at N(1) and N(2) with tBuCl affords the nitrenium cations [C

Language: Английский

Citations

15
Frustrated Lewis Pairs Comprising Nitrogen Lewis Acids for Si–H Bond Activation DOI
Idan Avigdori,

Alla Pogoreltsev,

Alexander Kaushanski

et al.

Angewandte Chemie, Journal Year: 2020, Volume and Issue: 132(52), P. 23682 - 23685

Published: Sept. 24, 2020

Abstract N‐heterocyclic nitrogen Lewis acids are a recent addition to the field of organic chemistry. Based on nitrenium cations, these where previously shown generate adducts when combined with appropriate bases. Herein, triazinium‐based acid was t Bu 3 P frustrated pair (FLP) capable cleaving, for first time, Si−H bonds in silanes. Whereas low yields were initially encountered owing insufficient acidity, new nitrenium‐based synthesized, and its superior acidity experimentally computationally confirmed. A FLP based this cleaved bond PhSiH , generating triazane product quantitative yield. This unprecedented N−H fully characterized by multinuclear NMR techniques single‐crystal X‐ray crystallography. class compounds, N‐H triazanes display potential capacity participate hydride transfer reactions.

Language: Английский

Citations

9
Electrochemical Reduction of Diarylketones and Aryl Alkenes DOI

Ce Bi,

Xiangyu Zhao,

Zhiqi Jia

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(9)

Published: March 20, 2023

Abstract The reduction of ketones or alkenes is an attractive and challenging task in organic chemistry has widespread applications the production fine chemicals, fragrances, pharmaceuticals, vitamins, functional materials. Classical methods usually require use potentially dangerous hydrogen reaction under high temperature pressure conditions, so environmentally friendly, economical, simple, safe are urgently needed. This paper innovatively reports a method for electrochemical diarylketones aryl mixed solvent system CH 3 CN/THF. proceeds smoothly, corresponding products obtained yields. mechanistic study shows that free radical reaction, reveals necessity CN solvent, which plays three roles proton donors, reactant at same time. Furthermore, yield gram‐scale experiment successfully confirmed potential industrial application this method.

Language: Английский

Citations

3
Nitrenium Salts in Intramolecular Lewis Pairs DOI Creative Commons
Idan Avigdori, Kuldeep Singh,

Alla Pogoreltsev

et al.

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2022, Volume and Issue: 649(4)

Published: Nov. 29, 2022

Abstract Herein we present the synthesis, full characterization and systematic investigation of intramolecular Lewis pairs incorporating acidic N‐heterocyclic nitrenium salts linked to phosphine bases. Intramolecular adducts frustrated (FLPs) were obtained, depending on different modification molecular structure. Several aryl alkyl groups utilized as substituents core naphthotriazinium components, which by an chain variable length. Whereas intermolecular adduct with a relatively weak donor (Ph 2 PMe) was not observed, corresponding version PR) detected both in dissociated pair form coordinated simultaneously. Additionally, one set modifications led unique rearrangement core, resulting fused heterocycle. The mechanism this analyzed computationally.

Language: Английский

Citations

4