A Coppoborylene Stabilized by Multicenter Covalent Bonding and Its Amphoteric Reactivity to CO DOI
Jin Hu,

Xiaopeng Xing,

Xuefeng Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: May 27, 2024

A cationic copper-stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three-center-two-electron metal-boron-metal covalent bonding interaction, displaying exceptional σ-acidity unparalleled π-donor capability for CO activation that outperforms all the known transition metal cations is comparable or even superior to documented base-trapped borylenes. Its neutral form represents monovalent boron compound with strongly reactive amphoteric center built on transition-metal-boron bonds, which inspires design synthesis members borylene family.

Language: Английский

Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions DOI Creative Commons
Md. Nasim Khan, Yara van Ingen,

Tribani Boruah

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13661 - 13695

Published: Jan. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Language: Английский

Citations

32
Recent progress on the functionalization of white phosphorus in China DOI Creative Commons
Xinlei Huangfu, Zhongzhen Wang, Yu Chen

et al.

National Science Review, Journal Year: 2024, Volume and Issue: 11(6)

Published: May 2, 2024

Direct synthesis of organophosphorus compounds from white phosphorus represents a significant but challenging subject, especially in the context ongoing efforts to comprehensively improve phosphorus-derived chemical industry driven by sustainability and safety concerns. China is world's largest producer phosphorus, creating demand for green transformation this crucial feedstock. This review provides an overview advancements activation Chinese research teams, focusing on direct construction P‒C/N/O/S/M bonds phosphorus. Additionally, we offer some insights into prospective directions future. paper aims attract more researchers engage area, stimulating follow-up exploration fostering enduring advances.

Language: Английский

Citations

11
Access to Bis-Silylene-Stabilized Group 13 Cations DOI
Moushakhi Ghosh, Prakash Panwaria, Srinu Tothadi

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

Herein, we report the isolation of pyridine moiety-functionalized SiNSi pincer-based bis-silylene ligand (1) and its reactivity toward various halide precursors (X = Br I) group 13 elements (M Al, Ga, In). This gave us straightforward access to pincer-coordinated cations (2–7). These complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear magnetic resonance spectroscopy (1H, 13C, 29Si), high-resolution mass spectrometry techniques. Their electronic properties were further analyzed with help quantum chemical calculations.

Language: Английский

Citations

1
Carbon dioxide capture and functionalization by bis(N-heterocyclic carbene)-borylene complexes DOI Creative Commons
Jun Fan,

An‐Ping Koh,

Chi‐Shiun Wu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 9, 2024

Derivatives of free monocoordinated borylenes have attracted considerable interest due to their ability exhibit transition-metal-like reactivity, in particular small molecules capture. However, such complexes are rare as the formation is either endergonic, or resulting adduct a transient intermediate that prone reaction. Here, we present synthesis two bis(N-heterocyclic carbene)-borylene capable capturing and functionalizing carbon dioxide. The capture subsequent functionalization CO2 by bis(NHC)-disilylamidoborylene 1 demonstrated bis(NHC)-isocyanatoborylene-carbon dioxide complex 3. Reversible observed using bis(NHC)-mesitylborylene 2, persistent bis(NHC)-mesitylborylene-carbon 4 can be stabilized hydrogen bonding with boric acid. reactions ammonia-borane aniline demonstrate captured further functionalized.

Language: Английский

Citations

6
Mechanistic Studies on the Bismuth‐Catalyzed Transfer Hydrogenation of Azoarenes DOI Creative Commons
Hye Won Moon, Feng Wang, Kalishankar Bhattacharyya

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Sept. 28, 2023

Organobismuth-catalyzed transfer hydrogenation has recently been disclosed as an example of low-valent Bi redox catalysis. However, its mechanistic details have remained speculative. Herein, we report experimental and computational studies that provide insights into a Bi-catalyzed azoarenes using p-trifluoromethylphenol (4) pinacolborane (5) hydrogen sources. A kinetic analysis elucidated the rate orders in all components catalytic reaction determined 1 (2,6-bis[N-(tert-butyl)iminomethyl]phenylbismuth) is resting state. In azobenzene 4, equilibrium between ⋅ [OAr]2 (Ar=p-CF3 -C6 H4 ) observed, thermodynamic parameters are established through variable-temperature NMR studies. Additionally, pKa -gated reactivity validating proton-coupled nature transformation. The ensuing crystallographically characterized, shown to be rapidly reduced presence 5. DFT calculations indicate rate-limiting transition state which initial N-H bond formed via concerted proton upon nucleophilic addition hydrogen-bonded adduct 4. These guided discovery second-generation catalyst, lower energy, leading at catalyst loadings cryogenic temperature.

Language: Английский

Citations

11
Bisgermylene-Stabilized Stannylone: Catalytic Reduction of Nitrous Oxide and Nitro Compounds via Element-Ligand Cooperativity DOI

Binglin Lei,

Fanshu Cao,

Ming Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17817 - 17826

Published: May 23, 2024

This study describes the synthesis, structural characterization, and catalytic application of a bis(germylene)-stabilized stannylone (

Language: Английский

Citations

4
Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases DOI

Weiwei Lv,

Yuyang Dai,

Rui Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 3, 2023

Abstract This report unveils an advancement in the formation of a Lewis superacid (LSA) and organic superbase by geometrical deformation organoboron species towards T‐shaped geometry. The boron dication [ 2 ] 2+ supported amido diphosphine pincer ligand features both large fluoride ion affinity (FIA>SbF 5 ) hydride (HIA>B(C 6 F 3 ), which qualifies it as hard soft LSA. unusual acidic properties are further showcased its ability to abstract from Et SiH AgSbF respectively, effectively catalyze hydrodefluorination, defluorination/arylation, well reduction carbonyl compounds. One two‐electron affords stable radical cation ]⋅ + borylene , respectively. former has extremely high spin density 0.798 e at atom, whereas latter compound been demonstrated be strong base (calcd. p K BH (MeCN)=47.4) theoretical experimental assessment. Overall, these results demonstrate geometric constraining empower central atom.

Language: Английский

Citations

10
An N-Phosphinoamidinato Borasilenide: A Vinyl Anion Containing a B=Si Double Bond DOI Creative Commons

Si Jia Isabel Phang,

Zhengfeng Zhang, Ming‐Der Su

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An N -phosphinoamidinato potassium borasilenide containing an anionic SiB double bond is a versatile building block for transferring BSi or B/Si atoms into inorganic and organic substrates.

Language: Английский

Citations

0
Copper-PMHS System-Enabled Reductive Cyclization of o-Aminobenzamides with CO2 as a Single-Carbon Synthon DOI
Jiang Nan, Lu Zhang,

Rui Cao

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chemical utilization of carbon dioxide (CO2) has emerged as a sustainable access for synthesizing high-value chemicals. Continuously designing the more practical reaction systems is large importance. Herein, an unprecedented and powerful copper-PMHS reductive system o-aminobenzamides with CO2 disclosed. Synthetically, diverse range quinazolinones (>70 examples) are rapidly assembled excellent functional group tolerance in good yields. Moreover, building other types heterocycles such benzothiazoles benzimidazoles also allowable. Mechanistically, differing from reported carbonylation cases, this finding represents scarce example single-carbon atom synthon PMHS system.

Language: Английский

Citations

0
Isolation of Silylene-Ligated Plumbyliumylidene and Diplumbyne DOI

Kainan Yu,

Fanshu Cao,

Xi Chen

et al.

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Language: Английский

Citations

0