(3+2) Annulation of 4‐Acetoxy Allenoate with Aldimine Enabled by AgF‐Assisted P(III)/P(V) Catalysis DOI
Jinlong Qian, Lijin Zhou,

Rouxuan Peng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 21, 2023

Abstract A phosphine‐catalyzed (3+2) annulation of 4‐acetoxy allenoate and aldimine with the assistance AgF is described. The success this reaction hinges on metathesis between enolate‐phosphonium zwitterion AgF, leading to a key intermediate comprising silver enolate fluorophosphorane P(V)‐moiety. former able undergo Mannich aldimine, whereas latter initiates cascade sequence AcO‐elimination/aza‐addition, thus furnishing P(III)/P(V) catalysis. By taking advantage enolate, preliminary attempt at an asymmetric variant was conducted combination achiral phosphine catalyst chiral bis(oxazolinyl)pyridine ligand (PyBox), giving moderate enantioselectivity.

Language: Английский

Ligand-enforced geometric constraints and associated reactivity in p-block compounds DOI

Tyler J. Hannah,

Saurabh S. Chitnis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 764 - 792

Published: Dec. 15, 2023

This review presents a group-wise summary of ligand enforced non-VSEPR geometries in compounds the p-block elements and discusses emergent consequences for reactivity.

Language: Английский

Citations

26

Metallomimetic C–F Activation Catalysis by Simple Phosphines DOI Creative Commons
Sara Bonfante, Christian Lorber, Jason M. Lynam

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2005 - 2014

Published: Jan. 11, 2024

Delivering metallomimetic reactivity from simple p-block compounds is highly desirable in the search to replace expensive, scarce precious metals by cheap and abundant elements catalysis. This contribution demonstrates that catalysis, involving facile redox cycling between P(III) P(V) oxidation states, possible using only simple, cheap, readily available trialkylphosphines without need enforce unusual geometries at phosphorus or use external oxidizing/reducing agents. Hydrodefluorination aminodefluorination of a range fluoroarenes was realized with good very yields under mild conditions. Experimental computational mechanistic studies show phosphines undergo oxidative addition fluoroaromatic substrate via Meisenheimer-like transition state form fluorophosphorane. undergoes pseudotransmetalation step silane, initial fluoride transfer P Si, give experimentally observed phosphonium ions. Hydride hydridosilicate counterion then leads hydridophosphorane, which reductive elimination product reform phosphine catalyst. behavior analogous many classical transition-metal-catalyzed reactions so rare example both functional mechanistically catalysis main-group element system. Crucially, reagents used are commercially, easy handle, making these realistic prospect wide academic industrial settings.

Language: Английский

Citations

13

Hydrogen splitting at a single phosphorus centre and its use for hydrogenation DOI
Deependra Bawari, Donia Toami, Kuldeep Jaiswal

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1261 - 1266

Published: June 27, 2024

Language: Английский

Citations

8

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

Reactivity of a Strictly T‐Shaped Phosphine Ligated by an Acridane Derived NNN Pincer Ligand DOI Creative Commons

Aaron J. King,

Josh Abbenseth, José M. Goicoechea

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(39)

Published: April 12, 2023

Abstract The steric tuning of a tridentate acridane‐derived NNN pincer ligand allows for the isolation strictly T‐shaped phosphine that exhibits ambiphilic reactivity. Well‐defined phosphorus‐centered reactivity towards nucleophiles and electrophiles is reported, contrasting with prior reports on this class compounds. Reactions oxidants are also described. latter result in two‐electron oxidation phosphorus atom from +III to +V accompanied by strong geometric distortion ligand. By contrast, cooperative activation E−H (HCl, HBcat, HOMe) bonds proceeds retention redox state. When using H 2 O as substrate, reaction results full disassembly its constituent atoms, highlighting potential platform small molecule reactions.

Language: Английский

Citations

14

Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene DOI Creative Commons
Yizhen Chen, Peifeng Su, Dongmin Wang

et al.

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

Published: May 29, 2024

Abstract Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons transient phosphinidenes. However, the synthesis such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies phosphanorcaradiene, in which one benzene rings flanking fluorenyl substituents intramolecularly dearomatized through attachment atom. It facilely obtained by reduction phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts synthetic equivalent phosphinidene. reacts trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. When treated two molar equivalents azide, iminophosphane bis(imino)phosphane isolated, Moreover, capable activating ethylene alkyne afford [1 + 2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceed smoothly at room temperature without presence transition metals. The driving force for these most likely ring-constraint three-membered PC 2 ring recovery aromaticity ring.

Language: Английский

Citations

6

Redox-active carborane clusters in bond activation chemistry and ligand design DOI

Bryce C. Nussbaum,

Amanda L. Humphries,

Gayathri B. Gange

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(66), P. 9918 - 9928

Published: Jan. 1, 2023

The icosahedral carborane cluster can accept two electrons and change from a closed closo -form to an open nido -form. This transformation unlocks the potential for bond activation chemistry, uranyl capture, stabilization of low-valent centers.

Language: Английский

Citations

13

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

Structural constraint effects on p-block elements: Recent advances DOI
Avijit Maiti, Ravi Yadav, Lutz Greb

et al.

Advances in inorganic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 261 - 299

Published: Jan. 1, 2023

Language: Английский

Citations

10

Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling DOI
Minghao Huang, Kunlong Li, Zichen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20432 - 20438

Published: July 9, 2024

The stibinidene ArSb

Language: Английский

Citations

4