AI Article Synopsis
- The reaction between bisboracumulene and excess tert-butylisocyanide leads to the formation of a complex where isocyanide binds to boron.
- The resulting compound features highly delocalized electrons across a conjugated π-network involving the CAAC and isocyanide ligands, challenging the typical depiction of boron's electron state.
- Heating this complex at 110°C produces a novel dicyanodiborene, which displays unexpected reduction behavior in cyclic voltammetry analysis, distinguishing it from typical diborenes.
Article Abstract
The reaction of the bisboracumulene (CAAC)2 B2 (CAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with excess tert-butylisocyanide resulted in complexation of the isocyanide at boron. Though this compound might be formally drawn with a lone pair on boron, these electrons are highly delocalized throughout a conjugated π-network consisting of the π-acidic CAAC and isocyanide ligands. Heating this compound to 110 °C liberated the organic periphery of both isocyanide ligands, yielding the first example of a dicyanodiborene. Cyclic voltammetry conducted on this diborene indicated the presence of reduction waves, making this compound unique among diborenes, which are otherwise highly reducing.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201412006 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Molecular-Scale Insights into the Heterogeneous Interactions between an -Terphenyl Isocyanide Ligand and Noble Metal Nanoparticles.
Nano Lett
January 2025
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0309, United States.
The structural and chemical properties of metal nanoparticles are often dictated by their interactions with molecular ligand shells. These interactions are highly material-specific and can vary significantly even among elements within the same group or materials with similar crystal structure. In this study, we surveyed the heterogeneous interactions between an -terphenyl isocyanide ligand and Au and Ag nanoparticles (NPs) at the single-molecule limit.
View Article and Find Full Text PDFExploring Stibanyl Ligand for Accessing Arsinidene and Arsaketene Adducts, and Phosphaketene.
Inorg Chem
January 2025
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China.
The salt metathesis reaction involving a diamine-based antimony chloride precursor with sodium arsaethynolate in the presence of PMe leads to the formation of stibanyl-functionalized PMe-arsinidene (). Detailed analyses through single-crystal X-ray diffraction and density functional theory of confirm the presence of covalent Sb-As bonds and reveal its polarized nature with a multiple-bond character. In contrast to the formation of complex , substituting PMe with xylyl isocyanide or 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene () produces an isocyanide-arsinidene adduct () and an -arsaketene complex (), respectively.
View Article and Find Full Text PDFAddition and Oxidation Reactivity of a Pentacoordinate Nickelacyclobutane.
Chemistry
December 2024
Organic Chemistry and Catalysis, Faculty of Science, Utrecht University, Institute for Sustainable and Circular Chemistry, Universitetisweg 99, 3584 CG, Utrecht, The, Netherlands.
Nickelacyclobutanes are reactive intermediates in catalytic cycles including cyclopropanation and insertion reactions. The stoichiometric study of these intermediates has shown that their reactivity is highly influenced by the coordination environment of the nickel center. A pentacoordinated nickelacyclobutane embedded in a diphosphine pincer ligand has been shown to selectively undergo various reactions with exogenous ligands, including [2+2] cycloreversion and carbene transfer to an isocyanide.
View Article and Find Full Text PDFMetal (M = Cr, Mo, W, Re) carbonyl complexes with porphyrin and carborane isocyanide ligands: light-induced oxidation and carbon oxide release for antitumor efficacy.
Biomater Sci
January 2025
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Bld. 1 Vavilov Street, 119334 Moscow, Russian Federation.
The tetrapyrrolic macrocycle as a scaffold for various chemical modifications provides broad opportunities for the preparation of complex multifunctional conjugates suitable for binary antitumor therapies. Typically, illumination with monochromatic light triggers the photochemical generation of reactive oxygen species (ROS) (photodynamic effect). However, more therapeutically valuable effects can be achieved upon photoactivation of tetrapyrrole derivatives.
View Article and Find Full Text PDFZn(II)-Stabilized Azo-Anion Radical-Catalyzed Dehydrogenative Synthesis of Olefins.
J Org Chem
December 2024
Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Botanic Garden, Howrah 711103, India.
Herein, we describe a Zn-catalyzed atom-economical, inexpensive, and sustainable method for preparing a broad spectrum of substituted olefins utilizing alcohols as the main precursor. Using a Zn(II) complex [ZnLCl] () of the redox-noninnocent ligand 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (), various ()-olefins were prepared in good yields by coupling alcohols with sulfones and aryl cyanides under an inert atmosphere. Under an aerial atmosphere, vinyl nitriles were isolated in up to 82% yield reacting alcohols with benzyl cyanides in the presence of .
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!