A Straightforward Synthetic Route to Monocyclic 1,3,2,4-Diazadiborinines DOI
Xin Yue, Linlin Wu, Hao Wang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 751 - 756

Published: Dec. 31, 2024

A novel straightforward synthetic route to monocyclic 1,3,2,4-diazadiborinines has been developed by the sequential reaction of NHC-coordinated iminoborane with bases and haloboranes (or borate). The first examples featuring different functional groups on two B atoms have synthesized structurally characterized. Further derivatization 4-bromophenyl-substituted 1,3,2,4-diazadiborinine also achieved, giving biphenyl-substituted 1,3,2,4-diazadiborinine. aromaticity these newly was studied theoretical calculations.

Language: Английский

Synthesis and reactivity of an N-heterocyclic carbene–stabilized diazoborane DOI
Chonghe Zhang, Christopher C. Cummins, Robert J. Gilliard

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6706), P. 327 - 331

Published: July 18, 2024

Diazo compounds and organic azides are widely used as reagents for accessing valuable molecules in multiple areas of fundamental applied chemistry. Their capacity to undergo versatile chemical transformations arises from the reactive nature an incipient dinitrogen molecule at terminal position. In this work, we report synthesis characterization N-heterocyclic carbene (NHC)-stabilized diazoborane-a boron-centered analog diazoalkanes. The diazoborane displays a strong tendency release dinitrogen, thus serving borylene source, analogy diazoalkanes nitrene sources, respectively. Also reminiscent diazoalkane azide reactivity, serves 1,3-dipole that undergoes uncatalyzed [3+2] cycloaddition with unactivated alkyne, affording five-membered heterocycle after two-step rearrangement.

Language: Английский

Citations

6
Stabilization of [(N5)2BX]2– and [(N5)2B2X2]2– (X = H, F, Cl, Br) by Conjugation and Hyperconjugation Effects DOI Creative Commons
Dongsheng Xiao, Qun Yu, Huan Yi

et al.

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

Published: Jan. 27, 2025

The isolation of nucleophilic boron bases has led to a paradigm shift in chemistry. Previous studies the bis(carbene) borylene complexes revealed that these compounds possess strong donor abilities, and their reaction inertness is due large steric hindrance between reagents reactant. In present study, we have theoretically studied [(N5)2BX]2- [(N5)2B2X2]2- (X = H, F, Cl, Br). Their electronic structures properties are discussed by using NBO, LOL, ELF methods. We found both π-conjugation hyperconjugation effects can effectively stabilize substituted anionic [(N5)2B2X2]2-. Substituents, especially X center through highly delocalized π-bonding, involving formally "empty" in-plane p orbitals atom. While halogen substituents high electron withdrawal ability, leading systems being less stable, suggest borinium anions [(N5)2BH]2- [(N5)2B2H2]2- as possible synthetic targets novel environmentally friendly catalysts.

Language: Английский

Citations

0
Syntheses, Geometric and Electronic Structures of Inorganic Cumulenes DOI Creative Commons

Jianqin Tang,

Chenyang Hu, Agamemnon E. Crumpton

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30778 - 30783

Published: Nov. 4, 2024

Molecular chains of two-coordinate carbon atoms (cumulenes) have long been targeted, due to interest in the electronic structure and applications extended π-systems, their relationship allotrope, carbyne. While formal (isoelectronic) B═N for C═C substitution has employed two-dimensional (2-D) materials, unsaturated one-dimensional all-inorganic "molecular wires" are unknown. Here, we report high-yielding synthetic approaches heterocumulenes containing a five-atom BNBNB chain, geometric which can be modified by choice end group. The diamido-capped system is bent at 2-/4-positions, natural resonance theory calculations reveal significant contributions from B═N(:)-B≡N-B forms featuring lone pair N (consistent with observed N-centered nucleophilicity). modification generate linear best described B═N═B═N═B involves chemical transformation capping groups (using B(C

Language: Английский

Citations

1
Vollständig anorganische sp‐Kettenliganden: Isoelektronische B/N‐Analoga von E. O. Fischers Alkinylcarbinen DOI

Luis Walther,

Krzysztof Radacki, Rian D. Dewhurst

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 15, 2024

Abstract Borylierung eines wolframgebundenen N 2 ‐Liganden und anschließende Halogenidabstraktion ermöglichen den Zugang zu einem kationischen Komplex mit bisher beispiellosen linearen NNBR‐Liganden. Dieser geht [3+2] Cycloadditionen Aziden ein eine unerwartete Kettenverlängerungsreaktion Iminoboran, was einer fünfatomigen B/N‐Kette führt. Diese beiden [NNBR]‐haltigen Komplexe, anorganische Analoga von E. O. Fischers Alkinylcarbinen, sind sehr seltene Beispiele für Moleküle, die rein Ketten sp ‐hybridisierten Atomen enthalten.

Citations

0
All‐Inorganic sp‐Chain Ligands: Isoelectronic B/N Analogues of E. O. Fischer's Alkynylcarbynes DOI

Luis Walther,

Krzysztof Radacki, Rian D. Dewhurst

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 15, 2024

Abstract Borylation of a tungsten‐bound N 2 ligand and halide abstraction provides access to cationic complex with an unprecedented linear NNBR ligand. This undergoes [3+2] cycloaddition azides, unexpected chain‐extension reaction iminoborane, leading five‐atom B/N chain. These two [NNBR]‐containing complexes, inorganic analogues E. O. Fischer's alkynylcarbynes, are very rare examples molecules containing all‐inorganic chains sp ‐hybridized atoms.

Language: Английский

Citations

0
Germaborene reactivity study – addition of carbon nucleophiles, cycloaddition reactions, coordination chemistry DOI Creative Commons

Christian Reik,

Lukas W. Jenner,

Hartmut Schubert

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(29), P. 11358 - 11366

Published: Jan. 1, 2024

Germaborene chemistry is presented: halide substitution by carbon nucleophiles, Cp*Al insertion into the B–Br bond, cycloaddition of CO 2 , dimethylbutadiene and selenium coordination CuBr, AuCl Fe(CO) 4 fragments at BGe double bond.

Language: Английский

Citations

0
A Straightforward Synthetic Route to Monocyclic 1,3,2,4-Diazadiborinines DOI
Xin Yue, Linlin Wu, Hao Wang

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 751 - 756

Published: Dec. 31, 2024

A novel straightforward synthetic route to monocyclic 1,3,2,4-diazadiborinines has been developed by the sequential reaction of NHC-coordinated iminoborane with bases and haloboranes (or borate). The first examples featuring different functional groups on two B atoms have synthesized structurally characterized. Further derivatization 4-bromophenyl-substituted 1,3,2,4-diazadiborinine also achieved, giving biphenyl-substituted 1,3,2,4-diazadiborinine. aromaticity these newly was studied theoretical calculations.

Language: Английский

Citations

0