Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding DOI Creative Commons
Nathanael H. Hunter, François P. Gabbaı̈

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 24, 2024

Abstract 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.

Language: Английский

A trimetallic bismuth(I)-based allyl cation DOI Creative Commons
Davide Spinnato,

Nils Nöthling,

Markus Leutzsch

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: 17(2), P. 265 - 270

Published: Jan. 6, 2025

Abstract The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis characterization a highly reduced salt featuring cationic core based on three contiguous Bi(I) centres. triatomic bismuth-based exhibits an configuration that mimics canonical description archetypical carbon-based π -allyl cation. Structural, spectroscopic theoretical analyses validate -delocalization between bismuth’s diffused 6 p orbitals, resulting bonding situation which atoms are interconnected by two bonds, formally possessing 1.5 bond order each. This defines complex as heaviest stable cation periodic table. Furthermore, demonstrate newly synthesized is able to act synthon for transfer forge other organobismuth complexes.

Language: Английский

Citations

1
Tetra-Cationic Distibane Stabilized by Bis(α-iminopyridine) and Its Reactivity DOI

Hritwik Haldar,

Satyabrata Das, Haakon T. A. Wiedemann

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Trendbericht Anorganische Chemie 2024: Hauptgruppen‐ und Molekülchemie DOI Open Access
Josh Abbenseth, Frank Tambornino

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(2), P. 46 - 55

Published: Jan. 31, 2025

Abstract Das erste heterobimetallische Dimetallocen; mit sterisch anspruchsvollen Liganden lassen sich einfach‐koordinierte Hauptgruppenverbindungen der Gruppen 13 bis 15 herstellen; neue Diazoverbindungen erlauben es, B‐R‐Einheiten und Kohlenstoffatome zu übertragen.

Citations

0
Comprehensive coordination chemistry of iminophosphonamides DOI Creative Commons
Bhupendra Goswami, Peter W. Roesky

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

Published: Jan. 1, 2025

This review summarizes the reported iminophosphonamide complexes of s-block, p-block, transition and f-block metals. Furthermore, recent development in field chiral metal is also discussed.

Language: Английский

Citations

0
A trimetallic bismuth-based allyl cation DOI Creative Commons
Davide Spinnato,

Nils Nöthling,

Markus Leutzsch

et al.

Published: April 9, 2024

The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis as well unique electronic structure fundamentals. In this work, we describe the synthesis and characterization a highly-reduced salt featuring cationic core based on three contiguous Bi(I) centers. triatomic bismuth-based holds an situation that mimics description archetypical carbonbased π-allyl cation. Structural, spectroscopic theoretical analyses validate π-delocalization between bismuth’s highly diffused 6p-orbitals, resulting 1.5 bond order Bi atoms. This places complex heaviest non-radioactive cation periodic table. Furthermore, demonstrate newly synthesized is able to act synthon for transfer forge other organobismuth complexes.

Language: Английский

Citations

1
Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding DOI Creative Commons
Nathanael H. Hunter, François P. Gabbaı̈

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 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.

Language: Английский

Citations

1
The Chlorido-Bismuth Dication: A Potent Lewis Acid Captured in a Hepta-Coordinate Species with a Stereochemically Active Lone Pair DOI Creative Commons
Ahmed Fetoh, Felipe Fantuzzi, Crispin Lichtenberg

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(26), P. 12089 - 12099

Published: June 20, 2024

The stabilization of simple, highly reactive cationic species in molecular complexes represents an important strategy to isolate and characterize compounds with uncommon or even unprecedented structural motifs properties. Here we report the synthesis, isolation, full characterization chlorido-bismuth dications, stabilized only by monodentate dimethylsulfoxide (dmso) ligands: [BiCl(dmso)

Language: Английский

Citations

0
Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding DOI Creative Commons
Nathanael H. Hunter, François P. Gabbaı̈

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 24, 2024

Abstract 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.

Language: Английский

Citations

0