The Effect of Carborane Substituents on the Lewis Acidity of Boranes DOI Creative Commons
Jason L. Dutton, Manjur O. Akram, Caleb D. Martin

et al.

Published: June 7, 2023

The Lewis acidity of primary, secondary, and tertiary boranes with phenyl, pentafluorophenyl, all three isomers icosahedral carboranes (ortho, meta, para) were investigated by computing their fluoride, hydride, ammonia affinities as well global electrophilicity indices LUMO energies. From these calculations, the substituent effects on follow trend ortho-carborane > meta-carborane para-carborane C6F5 C6H5.

Language: Английский

B(9)-OH-o-Carboranes: Synthesis, Mechanism, and Property Exploration DOI
Yan‐Na Ma,

Huazhan Ren,

Yanxuan Wu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7331 - 7342

Published: March 24, 2023

Herein, we present a chemically robust and efficient synthesis route for B(9)-OH-o-carboranes by the oxidation of o-carboranes with commercially available 68% HNO3 under assistance trifluoromethanesulfonic acid (HOTf) hexafluoroisopropanol (HFIP). The reaction is highly wide scope carboranes, selectivity B(9)/B(8) up to 98:2. success this transformation relies on strong electrophilicity oxidizability HNO3, promoted through hydrogen bonds Brønsted HOTf solvent HFIP. Mechanism studies reveal that o-carborane involves an initial electrophilic attack atom at most electronegative B(9) o-carborane. In transformation, B-H bond nucleophilic site, which different from substitution reaction, where boron site. Therefore, oxidation-reduction mild conditions in N(V) → N(III) H(-I) H(I). derivatization 9-OH-o-carborane was further examined, carboranyl group successfully introduced amino acid, polyethylene glycol, biotin, deoxyuridine, saccharide. Undoubtedly, approach provides selective way rapid incorporation carborane moieties into small molecules application neutron capture therapy, requires targeted delivery boron-rich groups.

Language: Английский

Citations

26
Avenue to novel o-carboranyl boron compounds – reactivity study of o-carborane-fused aminoborirane towards organic azides DOI Creative Commons
Junyi Wang,

Libo Xiang,

Xiaocui Liu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(13), P. 4839 - 4845

Published: Jan. 1, 2024

A range of novel o -carboranyl substituted boron compounds have been synthesized through reactions between an -carborane-fused aminoborirane and various organic azides. The reaction selectivity mechanisms were studied using DFT calculations.

Language: Английский

Citations

8
The Field of Main Group Lewis Acids and Lewis Superacids: Important Basics and Recent Developments DOI Open Access
Alexey Y. Timoshkin

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(1)

Published: Sept. 27, 2023

New developments in the field of Lewis acidity are highlighted, with focus novel acids and superacids group 2, 13, 14, 15 elements. Several important basics, illustrated by modern examples (classification Donor-Acceptor (DA) complexes, amphoteric nature any compound terms DA interactions, reorganization energies main role frontier orbitals) presented discussed. It is emphasized that phenomena general play vital different areas chemistry: from weak "atomophilic" interactions to complexes superacids.

Language: Английский

Citations

15
Persistent and Predominantly Localized Boron Radical from the Reduction of a Three‐Dimensional Analogue of NHC‐Stabilized Borafluorenium DOI Creative Commons

Libo Xiang,

Junyi Wang, Ivo Krummenacher

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(42)

Published: April 26, 2023

In this contribution, we reported the three-dimensional (3D) analogues of N-heterocyclic carbene (NHC)-stabilized 9-borafluorenium and 9-borafluorene radical. The radical was fully characterized by cyclic voltammetry (CV), UV-Vis absorption spectroscopy, electron paramagnetic resonance (EPR) single-crystal X-ray diffraction analyses. distinct boron-centered character corroborated DFT calculations EPR analysis.

Language: Английский

Citations

13
Bis(1‐Methyl‐ortho‐Carboranyl)Borane DOI Creative Commons
Manjur O. Akram, John R. Tidwell, Jason L. Dutton

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 20, 2023

The Lewis superacid, bis(1-methyl-ortho-carboranyl)borane, is rapidly accessed in two steps. It a very effective hydroboration reagent capable of B-H addition to alkenes, alkynes, and cyclopropanes. To date, this the first identified superacidic secondary borane most reactive neutral reagent.

Language: Английский

Citations

12
Borirenes and Boriranes: Development and Perspectives DOI Creative Commons
Junyi Wang, Qing Ye

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(11)

Published: Dec. 13, 2023

Strained compounds constitute a highly topical area of research in chemistry. Borirene and borirane both feature BC

Language: Английский

Citations

11
Synthesis and Stability of o-Carborane-Fused Phospholes DOI
Caixia Jia, Lili Wang, Zheng Duan

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Herein, we report that ArLi, formed in situ through the Li/Br exchange between aryl bromide and n-butyllithium, can undergo rapid intramolecular Li/H(Ccage–H) to functionalize o-carboranes. Based on this observation, a dual C–H lithiation reaction of 2- or 3-o-carboryl benzothiophenes was developed, series o-carborane-fused phospholes were synthesized by dilithio compounds with chlorophosphine. This is simple high chemical selectivity medium yields. It also be applied furan derivative. Stability studies demonstrated these phosphole derivatives are stable both trivalent coordination states for phosphorus. In contrast, their oxides sensitive moisture air susceptible attack nucleophiles, leading breakage Ccage-P bond. Computational results indicate newly generated rings have weak aromaticity.

Language: Английский

Citations

0
The Effect of Carborane Substituents on the Lewis Acidity of Boranes DOI
Manjur O. Akram, Caleb D. Martin, Jason L. Dutton

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(33), P. 13495 - 13504

Published: Aug. 10, 2023

The Lewis acidity of primary, secondary, and tertiary boranes with phenyl, pentafluorophenyl, all three isomers the C-substituted icosahedral carboranes (ortho, meta, para) was investigated by computing their fluoride, hydride, ammonia affinities as well global electrophilicity indices LUMO energies. From these calculations, it determined that substituent effects on follow trend ortho-carborane > meta-carborane para-carborane C6F5 C6H5.

Language: Английский

Citations

9
Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide DOI

Jared R. Riffle,

Tyler Hemingway,

Mark D. Smith

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(10), P. 4444 - 4450

Published: Jan. 1, 2024

Biscarborane dithiol and its bis(methyl)thioether feature exceedingly long intracluster C–C bond lengths, consistent with the increased π-backdonation of sulfur atom lone pairs into electron-accepting boron cluster.

Language: Английский

Citations

3
Carborane–arene fused boracyclic analogues of polycyclic aromatic hydrocarbons accessed by intramolecular borylation DOI Creative Commons
Yijie Li, Masilamani Tamizmani, Manjur O. Akram

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7568 - 7575

Published: Jan. 1, 2024

Carborane fused boron doped polycyclic aromatic hydrocarbons were accessed by dehydrobrominative and dehydrogenative borylation.

Language: Английский

Citations

3