A reaction of antimonytrichloride SbCl3 with potassium bis(terphenylimino)phosphide K[(TerN)2P] smoothly afforded a novel class of mixed diazadipnictanes, namely dichloro(diaza-phospha)stibane [Ter2N2P((III))Sb((III))Cl2], which is considered to exist as open chain-like and cyclic isomers in an equilibrium. [Ter2N2PSbCl2] is a versatile starting material for reduction and halide abstraction experiments. Halide abstraction led to the formation of a cyclic diazastibaphosphenium cation [P(μ-NTer)2SbCl](+). Upon reduction of [Ter2N2PSbCl2], the transient existence of the novel mixed biradicaloid [P(μ-NTer)2Sb] was proven by a trapping experiment with an alkyne, while reduction in the absence of trapping agents afforded the eight-membered heterocycle [Sb2-{μ-(TerN)2P}2]. This constitutional isomer of a dimerized biradicaloid features a bonding situation that indicates the presence of a donor-stabilized [Sb2](2+) ion.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c5dt02711j | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
The synthesis of a transient cationic phosphaborene [(Mes*)P=B(CAAC)]+ (Mes* = 2,4,6,-trit-tert-butylphenyl, CAAC = cyclic alkylamino carbene) by halide abstraction from the B-brominated analogue is reported. This species was found to undergo rapid and selective intramolecular aliphatic C-H bond activation to yield a phosphinoborenium cation, which undergoes facile deprotonation to give a cyclic base-stabilized phosphaborene. Computational investigation of the mechanism of C-H activation indicates a boron-centred activation route with an exceptionally low barrier of 8 kJ mol-1, followed by a nearly barrierless hydride migration from boron to phosphorus.
View Article and Find Full Text PDFHalogenated Trityl Cations as Easy-to-Access Super Electrophiles.
Angew Chem Int Ed Engl
January 2025
Freie Universität Berlin: Freie Universitat Berlin, Institut für Chemie und Biochemie, GERMANY.
Herein, we present the first easy-to-access synthesis of the perfluorotrityl cation (15F+) with commercial GaCl3 and the further functionalization of the para-fluorine atoms of 15F+ via halodefluorination using trimethylsilyl halides TMSX (X = Cl, Br). This gives access to equally reactive perhalogenated trityl derivatives (p-3Cl12F+ and p-3Br12F+), which can be handled at room temperature. The impact of the para-exchange on the electronic structure is determined by NMR and UV-Vis spectroscopy.
View Article and Find Full Text PDFSelective Ni(I)/Ni(III) Process for Consecutive Geminal C(sp)-C(sp) Bond Formation.
J Am Chem Soc
December 2024
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
Ni-catalyzed multicomponent cross-couplings have emerged as a powerful strategy for efficiently constructing complex molecular architectures from a diverse array of organic halides. Despite its potential, selectively forming multiple chemical bonds in a single operation, particularly in the realm of cross-electrophile coupling catalysis, remains a significant challenge. In this study, we have developed a consecutive open-shell reductive Ni catalysis, enabling the formation of two geminal C(sp)-C(sp) bonds from two stereoelectronically similar C(sp)-I reactants in conjunction with a methylene electrophile.
View Article and Find Full Text PDFBase-Free Borylation of Aryl Halides Enabled by Zn-Promoted Halide Abstraction.
Org Lett
December 2024
Department of Chemistry, The University of Texas at Austin, 100 East 24th Street, Austin, Texas 78712, United States.
Herein, we report the palladium-catalyzed borylation of aryl halides (iodides or bromides) under base-free conditions utilizing a commercially available Lewis acidic mediator, Zn(OTf). Under these conditions, an array of electronically and functional-group-diverse aryl iodides and bromides undergo borylation to afford the corresponding aryl boronic esters in ≤82% isolated yields. Mechanistic investigations are consistent with Zn(OTf) enabling transmetalation between a cationic Pd(II)-Ar intermediate and Bpin via halide abstraction.
View Article and Find Full Text PDFB(CF) Co-Catalyst Promotes Unconventional Halide Abstraction from Grubbs I to Enhance Reactivity and Limit Decomposition.
Organometallics
November 2024
Department of Chemistry and Biochemistry, Old Dominion University, 4501 Elkhorn Avenue, Norfolk, Virginia 23529, United States.
Ruthenium based Grubbs metathesis has become a commonplace reaction for synthetic chemists. Development of new generations of catalysts evolving from Grubbs I (GI) have led to greater stability, functional group compatibility, and superior reactivities. However, these advancements lead to increased costs.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!