The use of halogen bonding as a tool to construct a catalyst backbone is reported. Specifically, pyridyl- and iodotetrafluoroaryl-substituted phosphines were assembled in the presence of a rhodium(i) precursor to form the corresponding halogen-bonded complex . The presence of fluorine substituents at the iodo-containing supramolecular motif was not necessary for halogen bonding to occur due to the template effect exerted by the rhodium center during formation of the halogen-bonded complex. The halogen-bonded supramolecular complexes were successfully tested in the catalytic hydroboration of terminal alkynes.
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http://dx.doi.org/10.1039/c8sc00233a | DOI Listing |
Chemphyschem
January 2025
Shanxi University, Institute of Molecular Science, CHINA.
Delocalized multicenter bonds play a crucial role in clusters with a planar hypercoordinate center(s), making it difficult for highly electronegative elements, especially halogen atoms, to achieve the planar hypercoordinate arrangement. Herein, we introduce a star-like cluster Br6Li5-, whose global minimum contains a planar pentacoordinate bromine (ppBr). In this cluster, the central ppBr atom coordinates with five alkali metal Li atoms, which in turn bridge an equal number of electronegative Br atoms in the periphery, leading to the formation of the binary cluster Br6Li5-.
View Article and Find Full Text PDFInt J Mol Sci
January 2025
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The reaction involves an initial oxidative addition of the Se-Cl moiety to Au(I), followed by the nucleophilic addition of the pyridine fragment to the isonitrile's C≡N bond, furnishing a metallacycle. Importantly, this is the first example of the pyridine acting as a nucleophile towards metal-bound isonitriles.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Valladolid, Spain.
This article reports a theoretical study on the halogen exchange reactions YX + CHO → Y + XCHO (with Y = F, Cl, Br; X = Cl, Br, I) carried out at a high level of accuracy using coupled-cluster based methodologies including CCSD(T)-F12, CCSD(T)/CBS and CCSDT(Q). Most of the reactions are exothermic at room temperature, with the exception of the reactions FI + CHO → F + ICHO and ClI + CHO → Cl + ICHO. Exothermicity follows two concurrent trends established by the strength of the bonds being cleaved and formed: Y = F < Cl < Br (X-Y bond strength) and X = Cl > Br > I (C-X bond strength).
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden.
Direct cross-coupling reactions between two similar unactivated partners are challenging but constitute a powerful strategy for the creation of new carbon-carbon bonds in organic synthesis. [4]Dendralenes are a class of acyclic branched conjugated oligoenes with great synthetic potential for the rapid generation of structural complexity, yet the chemistry of [4]dendralenes remains an unexplored field due to their limited accessibility. Herein, we report a highly selective palladium-catalyzed oxidative cross-coupling of two allenes with the presence of a directing olefin in one of the allenes, enabling the facile synthesis of a broad range of functionalized [4]dendralenes in a convergent modular manner.
View Article and Find Full Text PDFChem Sci
January 2025
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, GBRCE for Functional Molecular Engineering, IGCME, Sun Yat-Sen University Guangzhou 510275 China
The separation of C cyclic hydrocarbons (benzene, cyclohexene, and cyclohexane) is one of the most challenging chemical processes in the petrochemical industry. Herein, we design and synthesize a new SOD-topology metal azolate framework (MAF) with aperture gating behaviour controlled by C-Br⋯N halogen bonds, which exhibits distinct temperature- and guest-dependent adsorption behaviours for benzene/cyclohexene/cyclohexane. More importantly, the MAF enables the efficient purification of benzene from its binary and ternary mixtures (selectivity up to 113 ± 2; purity up to 98% +), which is the highest record for benzene/cyclohexane/cyclohexene separation to date.
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