Isolable Pincer-type Dianionic Dialane(6) DOI
Wenjuan Wang,

Manling Bao,

Yuyang Dai

et al.

Organometallics, Journal Year: 2022, Volume and Issue: 41(6), P. 680 - 685

Published: March 16, 2022

Although pincer-type main group complexes have attracted considerable attention owing to their unique structures and intriguing reactivity, the isolation of dianionic dialane(6) is still elusive. Herein we report first synthesis species 4 bearing novel redox-active trinitrogen pincer ligands by reduction aluminum diiodide precursor 3 with excess potassium graphite. The structure has been investigated spectroscopic analysis, X-ray crystallography, density functional theory calculations, which reveal that possesses an Al–Al single covalent bond twisted trianionic ligands.

Language: Английский

Catalytic Activation of N2O at a Low-Valent Bismuth Redox Platform DOI Creative Commons
Yue Pang, Markus Leutzsch,

Nils Nöthling

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(46), P. 19473 - 19479

Published: Nov. 4, 2020

Herein we present the catalytic activation of N2O at a BiI⇄BiIII redox platform. The such kinetically inert molecule was achieved by use bismuthinidene catalysts, aided HBpin as reducing agent. protocol features remarkably mild conditions (25 °C, 1 bar N2O), together with high turnover numbers (TON, up to 6700) and frequencies (TOF). Analysis elementary steps enabled structural characterization catalytically relevant intermediates after O-insertion, namely rare arylbismuth oxo dimer unique monomeric hydroxide. This represents distinctive example main-group cycling for N2O.

Language: Английский

Citations

96
Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds DOI Creative Commons

Karina Chulsky,

Irina Malahov,

Deependra Bawari

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3786 - 3794

Published: Feb. 4, 2023

The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ3-P compound in the hexaphenyl-carbodiphosphoranyl-based pincer-type ligand (1+) are reported. 1+ reacts with electron-poor fluoroarenes via an oxidative addition-type reaction C-F bond to PIII-center, yielding new fluorophosphorane-type species (PV). This was used catalytic hydrodefluorination Ar-F bonds PhSiH3, C-N bond-forming cross-coupling reactions between aminosilanes. Importantly, these closely mimics mode action transition metal-based catalysts.

Language: Английский

Citations

34
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

25
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
Dual Reactivity of a Geometrically Constrained Phosphenium Cation DOI
Solomon Volodarsky, Deependra Bawari, Roman Dobrovetsky

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 13, 2022

A geometrically constrained phosphenium cation in bis(pyrrolyl)pyridine based NNN pincer type ligand (1

Language: Английский

Citations

35
Planar bismuth triamides: a tunable platform for main group Lewis acidity and polymerization catalysis DOI Creative Commons

Tyler J. Hannah,

W. Michael McCarvell,

Tamina Kirsch

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(17), P. 4549 - 4563

Published: Jan. 1, 2023

Geometric deformation in main group compounds can be used to elicit unique properties including strong Lewis acidity. Here we report on a family of planar bismuth(iii) complexes (cf. typically pyramidal structure for such compounds), which show geometric acidity that further tuned by varying the steric and electronic features triamide ligand employed. The structural dynamism bismuth was probed both solid solution phase, revealing at least three distinct modes intermolecular association. A modified Gutmann-Beckett method assess their electrophilicity employing trimethylphosphine sulfide addition triethylphosphine oxide as probes, providing insights into preference binding hard or soft substrates. Experimental studies were complemented computational assessment affinities dissection latter intrinsic bond strength energy components. results comparable triarylboranes, with added ability bind two bases simultaneously, reduced discrimination against We also study catalytic efficacy these ring opening polymerization cyclic esters ε-caprolactone rac-lactide. polymers obtained excellent dispersity values high molecular weights low catalyst loadings used. retain performance under industrially relevant conditions, suggesting they may useful less toxic alternatives tin catalysts production medical grade materials. Collectively, establish not only novel neutral platform acidity, but potentially valuable one catalysis.

Language: Английский

Citations

19
Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand DOI Creative Commons
Peter Coburger, Ana Guilherme Buzanich, Franziska Emmerling

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 6036 - 6043

Published: Jan. 1, 2024

The first pincer ligand featuring a strictly T-shaped pnictogen donor moiety was synthesised. PBiP ligand's redox activity facilitates unprecedented ambiphilic bonding of the Bi centre with transition metals through Bi(6p) orbital.

Language: Английский

Citations

8
Thermoneutral N−H Bond Activation of Ammonia by a Geometrically Constrained Phosphine DOI
Josh Abbenseth, Oliver P. E. Townrow, José M. Goicoechea

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23625 - 23629

Published: Sept. 3, 2021

A geometrically constrained phosphine bearing a tridentate NNS pincer ligand is reported. The effect of the geometric constraint on electronic structure was probed by theoretical calculations and derivatization reactions. Reactions with N-H bonds result in formation cooperative addition products. thermochemistry these transformations strongly dependent substrate, ammonia activation being thermoneutral. This represents first example molecular compound that reversibly activates via bond scission solution upon mild heating.

Language: Английский

Citations

38
LNL-Carbazole Pincer Ligand: More than the Sum of Its Parts DOI Creative Commons
George Kleinhans, Aino J. Karhu, Hugo Boddaert

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(13), P. 8781 - 8858

Published: June 23, 2023

The utility of carbazole in photo-, electro-, and medicinal applications has ensured its widespread use also as the backbone tridentate pincer ligands. In this review, aim is to identify illustrate key features LNL-carbazolide binding transition metal centers (with L = flanking donor moieties, e.g., C, N, P, O-groups) a systematic bottom-up progression marked benefits attainable from (i) rigid aromatic scaffold (modulable both 1,8- 3,6-positions), (ii) significant electronic effect central carbazole-amido metal, tunable sterics electronics (iii) L-moieties (iv) wingtip R-groups on L-donors, with their corresponding influence coordination geometry, d-electron configuration, resultant reactivity. Systematic implementation ligand design strategies not isolation, but combinatorial approach, showcased demonstrate potential for functional molecules that are only modulable adaptable wide-ranging (e.g., stereoselective (photo)catalysis, challenging small molecule activation, SET redox applications, even chemotherapeutics) an indication future research efforts anticipated stem versatile assembly, metals s-, p-, f-block elements.

Language: Английский

Citations

15
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