Tetra-Cationic Distibane Stabilized by Bis(α-iminopyridine) and Its Reactivity DOI

Hritwik Haldar,

Satyabrata Das, Haakon T. A. Wiedemann

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

The work establishes the salt of a tetra-cationic distibane, [L2Sb2][CF3SO3]4 = [1]2[OTf]4 (CF3SO3 OTf), stabilized by bis(α-iminopyridine) ligand L, defying Coulombic repulsion. synthetic approach involved dehydrocoupling reaction when mixture L and Sb(OTf)3 in 1:1 ratio was treated with Et3SiH/LiBEt3H as hydride source. Compound also achieved from [LSbCl][OTf]2 precursor using Et3SiH. Dissolution polar solvents unveiled formation persistent L-stabilized dicationic Sb(II) radical monomer [1][OTf]2, while addition Me3SiOTf regenerated dimer [1]2[OTf]4. homolytic cleavage Sb–Sb bond [1]24+ has manifested exchange reactions between Ph2Ch2 (Ch S, Se), giving [LSb(SPh)][OTf]2 [2][OTf]2 [LSb(SePh)][OTf]2 [3][OTf]2, respectively, acetonitrile. Reaction p-benzoquinone gave [L2Sb2(C6H4O2)][OTf]4 [4][OTf]4. An interesting oxygen atom insertion occurred 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to give [L2Sb2O][ OTf]4 [5][OTf]4. oxo-bridged compound [5][OTf]4 obtained exposure open air. strong Mn–Mn [Mn2(CO)10] could be cleaved reacting presence pyridine form [LSbMn(CO)5][ OTf]2 [6][OTf]2. On other hand, [Co2(CO)8] oxidative product [L2Sb2Co(CO)3][OTf]3 [7][OTf]3. compounds were characterized both solid solution states. Computational studies comprehensive understanding experimental findings.

Язык: Английский

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

Tyler J. Hannah,

Saurabh S. Chitnis

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 764 - 792

Опубликована: Дек. 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.

Язык: Английский

Процитировано

26
Oxidative Addition of Aryl Electrophiles into a Red-Light-Active Bismuthinidene DOI Creative Commons
Mauro Mato, Paolo Cleto Bruzzese, Fumiya Takahashi

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(34), С. 18742 - 18747

Опубликована: Авг. 21, 2023

The oxidative addition of aryl electrophiles is a fundamental organometallic reaction widely applied in the field transition metal chemistry and catalysis. However, analogous version based on main group elements still remains largely underexplored. Here, we report ability well-defined organobismuth(I) complex to undergo formal with wide range electrophiles. process facilitated by reactivity both ground excited states N,C,N-bismuthinidenes upon absorption low-energy red light.

Язык: Английский

Процитировано

25
Low-energy photoredox catalysis DOI
David C. Cabanero, Tomislav Rovis

Nature Reviews Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 11, 2024

Язык: Английский

Процитировано

18
Applications of bismuth-based nanoparticles for the removal of pollutants in wastewater: a review DOI
Shan Jiang, Yihang Zhang, Jianyu Gong

и другие.

Environmental Science Nano, Год журнала: 2024, Номер 11(4), С. 1332 - 1367

Опубликована: Янв. 1, 2024

This review discusses the characteristics and synthesis methods of Bi-based NPs. It delves into removal efficiency in wastewater, emphasizing traditional/emerging strategies to enhance performance, mechanisms, toxicology, challenges.

Язык: Английский

Процитировано

13
Transient Triplet Metallopnictinidenes M–Pn (M = PdII, PtII; Pn = P, As, Sb): Characterization and Dimerization DOI Creative Commons
Marc C. Neben,

Nils Wegerich,

Tarek Al Said

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity this important class transient intermediates has attributed their electronic structures, particularly the accessibility triplet vs singlet states. In contrast, structure trends along heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report synthesis series metallodipnictenes, {M–Pn═Pn–M} (M PdII, PtII; P, As, Sb, Bi) characterization metallopnictinidene intermediates, {M–Pn} for Sb. Structural, spectroscopic, computational analysis revealed spin ground states metallopnictinidenes with characteristic series. comparison nitrene, pnictinidenes exhibit lower-lying state SOMOs excited states, thus suggesting increased electrophilic reactivity. Furthermore, splitting magnetic microstates is beyond phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Язык: Английский

Процитировано

2
Lewis Superacidic Heavy Pnictaalkene Cations: Comparative Assessment of Carbodicarbene-Stibenium and Carbodicarbene-Bismuthenium Ions DOI
Levi S. Warring, Jacob E. Walley, Diane A. Dickie

и другие.

Inorganic Chemistry, Год журнала: 2022, Номер 61(46), С. 18640 - 18652

Опубликована: Ноя. 9, 2022

We report a comprehensive assessment of Lewis acidity for series carbone-stibenium and -bismuthenium ions using the Gutmann-Beckett (GB) method. These new antimony bismuth cations have been synthesized by halide abstractions from (CDC)PnBr3 [(pyCDC)PnBr2][Br] (CDC = carbodicarbene; Pn Sb or Bi; py pyridyl). The reaction (CDC)SbBr3 (1) with one two equivalents AgNTf2 (NTf2 bis(trifluoromethanesulfonyl)imide) AgSbF6 gives stibaalkene mono- dications form [(CDC)SbBr3-n][A]n (2-4; n 1,2; A NTf2 SbF6). trication [(CDC)2Sb][NTf2]3 (5) was also isolated collectively these molecules fill gap among cationic pnictaalkenes. are compared to related CDC-bismaalkene complexes 6-9. With goal preparing highly acidic compounds, tridentate bis(pyridine)carbodicarbene (pyCDC) used as ligand access (10, 12) trications [(pyCDC)Pn][NTf2]3 (Pn (11), Bi (13)), forgoing need second CDC in synthesis 5. bonding situation is elucidated through electron density energy decomposition analyses combination natural orbital chemical valence theory. In each complex, there exists CDC-Pn double interaction, consisting strong σ-bond weaker π-bond, whereby π-bond gradually strengthens increase charge complex. Notably, [(CDC)SbBr][NTf2]2 (4) has an acceptor number (AN) (84) that comparable quintessential acids such BF3, tricationic pnictaalkene 11 13 exhibit ANs 109 Sb) 84 Bi), respectively, which highest values reported any cation. Moreover, calculated fluoride ion affinities (FIAs) 99.8 94.3 kcal/mol, larger than SbF5 (85.1 kcal/mol), suggest superacids.

Язык: Английский

Процитировано

36
Mechanism of the Aryl–F Bond-Forming Step from Bi(V) Fluorides DOI
Oriol Planas, Vytautas Pečiukėnas, Markus Leutzsch

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(32), С. 14489 - 14504

Опубликована: Авг. 3, 2022

In this article, we describe a combined experimental and theoretical mechanistic investigation of the C(sp

Язык: Английский

Процитировано

32
Triplet bismuthinidenes featuring unprecedented giant and positive zero field splittings DOI Creative Commons
Mengyuan Wu, Wang Chen, Dongmin Wang

и другие.

National Science Review, Год журнала: 2023, Номер 10(10)

Опубликована: Июнь 10, 2023

Isolation of triplet pnictinidenes, which bear two unpaired electrons at the pnictogen centers, has long been a great challenge due to their intrinsic high reactivity. Herein, we report syntheses and characterizations bismuthinidenes MsFluindtBu-Bi (3) MsFluind*-Bi (4) stabilized by sterically encumbered hydrindacene ligands. They were facilely prepared through reductions corresponding dichloride precursors with 2 molar equivalents potassium graphite. The structural analyses revealed that 3 4 contain one-coordinate bismuth atom supported Bi-C single σ bond. As consequence, remaining Bi 6p orbitals are nearly degenerate, possess ground states. Experimental multinuclear magnetic resonance, magnetometry near infrared spectroscopy coupled wavefunction based ab initio calculations concurred evidence there exist giant positive zero field splittings (>4300 cm-1) in S = 1 Hence even room temperature systems almost exclusively populate lowest-energy nonmagnetic Ms 0 level, renders them seemingly diamagnetic.

Язык: Английский

Процитировано

24
Dihydrogen and Ethylene Activation by a Sterically Distorted Distibene DOI Creative Commons
Yue Pang, Markus Leutzsch,

Nils Nöthling

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 2, 2023

Herein, we report the synthesis of a sterically distorted distibene ([4]2 ) and its transition-metal-like reactivity towards two fundamental feedstock chemicals: H2 ethylene. Although [4]2 exhibits an unusually long Sb=Sb distance noticeable backbone distortion in solid state, NMR data suggest that remains predominantly as dimer solution, even at high temperatures. However, it was proposed elusive toward ethylene results from reversible dissociation into transient stibinidene ([4]), which could be observed by spectroscopic techniques.

Язык: Английский

Процитировано

22
1,3‐Imidazole‐Based Mesoionic Carbenes and Anionic Dicarbenes: Pushing the Limit of Classical N‐Heterocyclic Carbenes DOI Creative Commons
Rajendra S. Ghadwal

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Май 3, 2023

Classical N-heterocyclic carbenes (NHCs) featuring the carbene center at C2-position of 1,3-imidazole framework (i.e. C2-carbenes) are well acknowledged as very versatile neutral ligands in molecular materials sciences. The efficiency and success NHCs diverse areas is essentially attributed to their persuasive stereoelectronics, particular potent σ-donor property. with unusual C4 (or C5) position, so-called abnormal (aNHCs) or mesoionic (iMICs), however superior σ-donors than C2-carbenes. Hence, iMICs have substantial potential sustainable synthesis catalysis. main obstacle this direction rather demanding synthetic accessibility iMICs. aim review article highlight recent advances, particularly by author's research group, accessing stable iMICs, quantifying properties, exploring applications In addition, viability use vicinal C4,C5-anionic dicarbenes (ADCs), also based on an framework, presented. As will be apparent following pages, ADCs hold potentials pushing limit classical enabling access conceptually new main-group heterocycles, radicals, catalysts, sets, more.

Язык: Английский

Процитировано

21