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Synthesis and Characterization of a Non-planar Cyclophenylene on Au(111).
Chemistry
January 2025
Centro de Investigacion en Nanomateriales y Nanotecnologia, -, 33940, El Entrego, SPAIN.
We report the surface-assisted synthesis of a non-planar cyclophenylene derivative containing four meta- and two para- connected phenylene moieties on Au(111), via hierarchical Ullmann coupling of a 1,10-dibrominated angular [3]phenylene and subsequent C-C bond cleavage at the four-membered rings. Scanning tunneling microscopy and spectroscopy (STM/STS) were used for the characterization of its chemical structure and electronic properties. Density functional theory (DFT) calculations support the experimental observations.
View Article and Find Full Text PDFThe kinetics of sulfur transfer from titanocene (poly)sulfides (CpTiS, CpTiSCMe, CpTi(SAr), CpTiCl(SAr)) to sulfenyl chlorides (SCl, RSCl) have been investigated by a combination of stopped-flow UV-Vis/NMR reaction monitoring, titration assays, numerical kinetic modelling and KS-DFT calculations. The reactions are rapid, proceeding to completion over timescales of milliseconds to minutes, a sequence of two S-S bond-forming steps ( , ). The archetypical polysulfides CpTiS (1a) and CpTiSC(Me) (2a) react with disulfur dichloride (SCl) through rate-limiting intermolecular S-S bond formation ( ) followed by a rapid intramolecular cyclization ( , with ≫ [RSCl]).
View Article and Find Full Text PDFNitrogen Atom Transfer Enables the (5+1) Annulation Reaction to Access Aminoisoquinolines.
Org Lett
June 2023
Medicinal & Process Chemistry Division and CSIR-Central Drug Research Institute, Lucknow 226031, U.P., India.
Herein, a catalytic synthetic transformation offering a series of -NH group-bearing aminoisoquinolines with moderate to good yields has been showcased. Interestingly, the nitrogen atom of the isoquinoline ring is coming from the reaction medium upon metal-assisted C≡N bond cleavage. Moreover, this (5+1) annulation reaction shows broad substrate variation.
View Article and Find Full Text PDFDinitrogen Activation by Dihydrogen and Quaternary Cluster Anions AuNbBO: Nb- and B-Mediated N Activation and Au-Assisted Nitrogen Transfer.
J Phys Chem Lett
May 2022
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
Nitrogen fixation and hydrogenation are important issues in chemistry and industry. Herein, we used mass spectrometry and quantum chemical calculations to identify the quaternary AuNbBO anions that can efficiently activate N and H to form imido (or amido) units in the products AuNbBONH under thermal collision conditions. In these reactions, Nb and B atoms work in synergy to dissociate N and the Au atom acts as a reducing agent, which facilitates the removal of one activated N atom for the following hydrogenation process; generation of three-centered, two-electron bonds facilitates N activation and N transformation.
View Article and Find Full Text PDFNovel binuclear and trinuclear metal (II) complexes: DNA interactions and in vitro anticancer activity through apoptosis.
J Inorg Biochem
August 2019
College of Material and Chemical Engineering, Henan University of Urban Construction, Henan 467036, China. Electronic address:
A water soluble trinuclear copper(II) complex and a binuclear cobalt(II) complex, namely Cu(ppbm)(SO) (1) and Co(ppbm)(NO) (2) (ppbm = 2-(pyridin-2-yl)-1-(pyridin-3-ylmethyl)- 1H-benzo[d]imidazole), have been successfully synthesized and characterized by elemental analysis, IR Spectroscopy, electrospray ionization mass spectra (ESI-MS). The interaction of the new complexes with DNA has been explored using spectroscopy methods, indicating that the complexes 1 and 2 bind to DNA via noncovalent interactions. DNA cleavage experiment suggested that the complex 1 exhibits efficient DNA cleavage activities in the presence of ascorbate (Asc), hydrogen peroxide may serve as the major cleavage active species.
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