An unprecedented tellurabenziporphyrin containing C, N, and Te donor atoms was synthesized by condensing benzitripyrrane and tellurophene diol under acid catalyzed conditions. The tellurabenziporphyrin readily forms a Pd(II) complex when treated with PdCl in CHCl/CHCN. The crystal structures of tellurabenziporphyrin and its Pd(II) complex revealed that the benzene ring hinders the π-electron delocalization. An unusual five-membered ring formed inside the macrocycle due to the strong interaction between "Te" and "N" in the Pd(II) complex.
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http://dx.doi.org/10.1021/acs.orglett.7b03715 | DOI Listing |
ACS Catal
January 2025
Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg, 1, 8093 Zurich, Switzerland.
Buchwald-Hartwig (BH) aminations are crucial for synthesizing arylamine motifs in numerous bioactive molecules and fine chemicals. While homogeneous palladium complexes can be effective catalysts, their high costs and environmental impact motivate the search for alternative approaches. Heterogeneous palladium single-atom catalysts (SAC) offer promising recoverable alternatives in C-C cross-couplings.
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January 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
C-H activation is the most direct way of functionalizing organic molecules. Many advances in this field still require specific directing groups to achieve the necessary activity and selectivity. Developing C-H activation reactions directed by native functional groups is essential for their broad application in synthesis.
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January 2025
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR 6302 CNRS, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France.
Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.
View Article and Find Full Text PDFMolecules
December 2024
Institute of Chemistry, Faculty of Science and Technology, Jan Dlugosz University in Czestochowa, Armii Krajowej 13/15, 42-200 Czestochowa, Poland.
This study investigates the structural, vibrational, and biological properties of novel palladium(II) and platinum(II) complexes with 5-chloro-7-azaindole-3-carbaldehyde (5ClL) and 4-chloro-7-azaindole-3-carbaldehyde (4ClL) ligands. Infrared and Raman spectroscopy, combined with DFT (ωB97X-D) calculations, provided valuable information about metal-ligand interactions, the or conformation of the aldehyde group in the ligands, and the presence of isomers in the metal complexes obtained in the solid state. tests were used to evaluate the antiproliferative activity of the novel complexes against several cancer cell lines, including ovarian cancer (A2780), cisplatin-resistant ovarian cancer (A2780cis), colon cancer (HT-29), and triple-negative breast cancer (MDA-MB-231), as well as normal mouse fibroblasts (BALB/3T3).
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December 2024
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Since the 1980s, pressure-sensitive paint (PSP) has been used as an optical pressure sensor for measuring surface pressure on aircraft models in wind tunnels. Typically, PSPs have utilized platinum(II)-5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)-porphyrin due to its high pressure sensitivity, phosphorescence lifetime of ∼50 μs, reasonable quantum yield of emission, and resistance to photo-oxidation. This work investigates the photophysics and electronic structure of metal complexes of 5,10,15,20-tetrakis(2,3,4,5,6-pentafluorophenyl)-porphyrin, namely, Zn(II), Pd(II), and Ir(III), as potentially improved luminophores for polymer-based PSPs.
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