Charge Makes a Difference: Molecular Ionic Bismuth Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: Feb. 27, 2023

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.

Language: Английский

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Bioactive Bismuth Compounds: Is Their Toxicity a Barrier to Therapeutic Use?

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(3), P. 1600 - 1600

Published: Jan. 27, 2024

Bismuth compounds are considered relatively non-toxic, with their low solubility in aqueous solutions (e.g., biological fluids) being the major contributing factor to this property. derivatives widely used for treatment of peptic ulcers, functional dyspepsia, and chronic gastritis. Moreover, properties bismuth have also been extensively explored two main fields action: antimicrobial anticancer. Despite clinical interest bismuth-based drugs, several side effects reported. In fact, excessive acute ingestion bismuth, or abuse an extended period time, can lead toxicity. However, evidence has demonstrated that discontinuation these usually reverses toxic effects. Notwithstanding, continuously growing use products suggests it is indeed part our environment daily lives, which urges a more in-depth review investigation into its possible undesired activities. Therefore, aims update pharmaco-toxicological compounds. A special focus will be given vitro, vivo, studies exploring

Language: Английский

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Effects of Hypervalent Bismuth on Electronic Properties of the Azobenzene Tridentate Ligand and Roles of Lewis Acidity in Controlling Optical Properties

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(11), P. 4590 - 4597

Published: March 3, 2023

Organobismuth compounds have been studied in various fields, including electronic states, pnictogen bonds, and catalysis. Among them, one of the unique states element is hypervalent state. So far, many issues regarding structures bismuth revealed; meanwhile, influence on properties π-conjugated scaffolds still vailed. Here, we synthesized compound, BiAz, by introducing into azobenzene tridentate ligand as a scaffold. The was evaluated from optical measurements quantum chemical calculations. introduction revealed three significant effects: first, shows position-dependent electron-donating electron-accepting effects. Second, BiAz can larger effective Lewis acidity than tin compound derivatives reported our previous research. Finally, coordination dimethyl sulfoxide transformed similar to compounds. data calculations showed that scaffold were able be changed bismuth. To best knowledge, first demonstrate should new methodology for controlling molecules developing sensing materials.

Language: Английский

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Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand

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

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Expanding the scope of bis(catecholato)germane catalysis: hydrosilylation, hydroboration, Friedel–Crafts alkylation and oligomerization

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(30), P. 10363 - 10371

Published: Jan. 1, 2023

Various applications of bis(catecholato)germanes in catalysis were examined. The hydrosilylation benzaldehydes, hydroboration phenylacetylene derivatives, and Friedel-Crafts alkylation using arylalkenes either diphenylamine or anisole was achieved. Furthermore, the recently reported oligomerization α-methylstyrene catalyzed by with weak donor ligands examined further. formation a trimer species observed DCM. VTNA Hammett analyses reaction conducted an updated mechanism for bis(catecholato)germane is proposed.

Language: Английский

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Environmentally Friendly Organic Synthesis Using Bismuth(III) Compounds: A Mini Review

Structure and bonding, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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Bismuth-based Lewis acidity

Advances in inorganic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 237 - 260

Published: Jan. 1, 2023

Language: Английский

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Bismuth‐Catalyzed Amide Reduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 7, 2023

In this article we report that a cationic version of Akiba's BiIII complex catalyzes the reduction amides to amines using silane as hydride donor. The catalytic system features low catalyst loadings and mild conditions, en route secondary tertiary aryl- alkylamines. tolerates functional groups such alkene, ester, nitrile, furan thiophene. Kinetic studies on reaction mechanism result in identification network with an important product inhibition is agreement experimental profiles.

Language: Английский

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Theoretical Study on Bismuth(III) Catalysts for Synthesis of Phenylsulfonyl Fluoride: Reasons of Their Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2758 - 2774

Published: Feb. 7, 2024

Bismuth(III) complex with diarylsulfone ligand (diAr-SO2) is a non-transition metal catalyst reported recently for the synthesis of arylsulfonyl fluorides. We investigated this catalytic reaction using DFT and SCS-MP2 calculations geometries energies, respectively. This occurs through transmetalation between (BF4)Bi(diAr-SO2) phenylboronic acid (PhB(OH)2), SO2 insertion into Bi–Ph bond (Ph)Bi(diAr-SO2), fluorination PhOSO group (PhOSO)Bi(diAr-SO2) by Selectfluor. The rate-determining step diAr-SO2 (CH3, CH3) (CF3, CF3) but either or CF3), where (R1, R2) means has R1 R2 substituents on its aryl groups. activation energy (ΔG°‡) increases in order < CF3). increasing consistent experimentally observed substituent effects activity. difficult to occur absence potassium phosphate (K3PO4) moderate presence K3PO4 because activates B–Ph σ-bond stabilizes dissociating B(OH)2 moiety electrostatic interaction. play an important role transmetalation; when strongly interacts Bi(diAr-SO2) species form overly stable adduct enlarge considerably ΔG°‡ value. When CH3), stabilization similar each other, destabilization more largely upon going asymmetric transition state from case than case. Thus, use favorable transmetalation. (Ph)Bi(diAr-SO2) value, whereas sulfone (SO2) replaced CH2 group. via nucleophilic attack Ph SO2. However, not most reactive only HOMO also factors such as Biδ+–(C6H3R)δ− (R = CH3 dipole moment Bi–C6H3R strength participate determining reactivity C6H3R part diArSO2. value extremely negative ΔG° Its hardly depends diAr-SO2. are key activity bismuth catalyst.

Language: Английский

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NCN-pincer organopnictogen(iii) bis(aryloxides)

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(12), P. 5523 - 5529

Published: Jan. 1, 2024

New hypercoordinated organopnictogen( iii ) bis(aryloxides), ArPn(SC 6 H 3 R 2 -2,6) (Pn = Sb, Bi; Ar NCN-pincer ligand; i Pr, OMe), have been prepared and their solution solid state structures investigated.

Language: Английский

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