Poly-pnictogen bonding: trapping halide ions by a tetradentate antimony(iii) Lewis acid

Chemical Science, Год журнала: 2023, Номер 14(46), С. 13551 - 13559

Опубликована: Янв. 1, 2023

A tetradentate host system with four CC–Sb(C 2 F 5 ) functions binds halide ions in a distorted square planar coordination. Experimental and calculated structures reveal complex interplay of attractive pnictogen bonding Coulomb repulsion.

Язык: Английский

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Recent advances in the stabilization of monomeric stibinidene chalcogenides and stibine chalcogenides

Dalton Transactions, Год журнала: 2024, Номер 53(20), С. 8524 - 8534

Опубликована: Янв. 1, 2024

The synthetic strategies employed to isolate monomeric stibinidene chalcogenides (RSbCh) and stibine (R 3 SbCh) are discussed, a perspective on the outcomes future directions of this exciting area is provided.

Язык: Английский

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Direct O₂ Activation by Ligand-Constrained Pnictogen Complexes: Contrasting Mechanisms and OAT Reactivity across the P, Sb, and Bi Triad

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

Язык: Английский

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Charge Makes a Difference: Molecular Ionic Bismuth Compounds

Angewandte Chemie, Год журнала: 2023, Номер 135(24)

Опубликована: Фев. 27, 2023

Abstract Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable methods, as well development promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities they show an intriguing spectrum properties that is yet to be fully exploited: a soft character, rich coordination chemistry, availability broad variety oxidation states (at least +V −I) formal charges +3 −3) at Bi atoms, reversible switching between multiple states. All this paired with status non‐precious (semi−)metal good tendency towards low toxicity. Recent findings some these only come into reach, or can substantially optimized, when charged are specifically addressed. In review, essential contributions synthesis, analyses, utilization ionic highlighted.

Язык: Английский

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What Distinguishes the Strength and the Effect of a Lewis Acid: Analysis of the Gutmann–Beckett Method

Angewandte Chemie, Год журнала: 2021, Номер 134(4)

Опубликована: Ноя. 10, 2021

Abstract IUPAC defines Lewis acidity as the thermodynamic tendency for pair formation. This strength property was recently specified global (gLA), and is gauged example by fluoride ion affinity. Experimentally, usually evaluated effect on a bound molecule, such induced 31 P NMR shift of triethylphosphine oxide in Gutmann–Beckett (GB) method. type scaling called effective (eLA). Unfortunately, gLA eLA often correlate poorly, but reason this unknown. Hence, acid are two distinct properties, they granted interchangeably. The present work analyzes thermodynamic, specific, London dispersion effects GB numbers 130 acids theory experiment. deformation energy identified prime cause critical deviation between its correction allows unification first time.

Язык: Английский

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Geminal Bimetallic Coordination of a Carbone to Main-Group and Transition Metals

Chemical Communications, Год журнала: 2024, Номер 60(14), С. 1880 - 1883

Опубликована: Янв. 1, 2024

The first examples of geminal bimetallic carbone coordination featuring main group metals have been isolated.

Язык: Английский

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Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs

Dalton Transactions, Год журнала: 2024, Номер 53(28), С. 11762 - 11768

Опубликована: Янв. 1, 2024

The reactions of the frustrated Lewis pair (F

Язык: Английский

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A Sterically Accessible Monomeric Stibine Oxide Activates Organotetrel(IV) Halides, Including C–F and Si–F Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19350 - 19359

Опубликована: Июль 3, 2024

Phosphine oxides and arsine are common laboratory reagents with diverse applications that stem from the chemistry exhibited by these monomeric species. Stibine are, in contrast, generally dimeric or oligomeric species because of reactivity-quenching self-association highly polarized stiboryl (Sb=O/Sb+–O–) group. We recently isolated Dipp3SbO (Dipp = 2,6-diisopropylphenyl), first example a kinetically stabilized stibine oxide, which exists as bench-stable solid bears an unperturbed Herein, we report isolation Mes3SbO (Mes mesityl), less bulky substituents maintain nature compound but unlock access to wider range reactivity at group relative Dipp3SbO. was found be potent Lewis base formation adducts main-group acids PbMe3Cl SnMe3Cl. The accessible acidity Sb atom results change GeMe3Cl, SiMe3Cl, CPh3Cl. With species, formally adds E–Cl (E Ge, Si, C) bond across unsaturated form 5-coordinate stiborane. biphilicity is sufficiently activate even C–F Si–F bonds C(p-MeOPh)3F SiEt3F, respectively. These mark significant contribution increasingly rich literature on polar, motifs. Furthermore, highlight utility kinetic stabilization approach unusual bonding motifs unquenched can leveraged for small-molecule activation.

Язык: Английский

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Crystallographic evidence for a continuum and reversal of roles in primary–secondary interactions in antimony Lewis acids: applications in carbonyl activation

Chemical Communications, Год журнала: 2022, Номер 58(78), С. 11009 - 11012

Опубликована: Янв. 1, 2022

Primary and secondary interactions form the basis of substrate activation in Lewis-acid mediated catalysis, with most activations occurring at binding site. We explore two series antimony cations, [(NMe2CH2C6H4)(mesityl)Sb]+ (A) [(NMe2C6H4)(mesityl)Sb]+ (B), by coordinating ligands varying nucleophilicity position trans to N-donor. The decreased incoming leads reversal from a primary bond interaction A, whereas constrained N-coordination B diminishes border between bonding. Investigations on carbonyl olefin metathesis reactions reduction demonstrate increased reactivity Lewis acid when occurs

Язык: Английский

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Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 24, 2024

Our interest in the design of heavy pnictogen-based Lewis acids for anion trafficking across biological membrane mimics has led us to investigate trivalent bismuthenium cations as chloride transporters. Here, we describe two chlorodiarylbismuthines, elaborated on a peri-substituted naphthalene backbone and stabilized by an adjacent thio- or seleno-ether functionality that engages bismuth center Ch→Bi interaction (Ch=chalcogen). These new derivatives are stable aqueous environment readiliy transport anions phospholipid-based vesicles loaded with KCl. In addition establishing use such motifs transport, this investigation shows acidity, lipophilicity, thus properties depend nature chalcogen.

Язык: Английский

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