Related Experiment Video
Updated: Oct 2, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Expanded Mercaptocalixarenes: A New Kind of Macrocyclic Ligands for Stabilization of Polynuclear Thiolate Clusters
Frederik Schleife1, Clément Bonnot2, Jean-Claude Chambron2,3
1Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103, Leipzig, Germany.
Abstract:
The syntheses and properties of expanded 4-tert-butyl-mercaptocalix[4]arenes, in which the methylene linkers are replaced by -CH2 NRCH2 - or -CH2 NRCH2 - and -CH2 NRCH2 CH2 CH2 NRCH2 - units, are described. The new macrocycles were obtained in a step-wise manner, utilizing fully protected, i. e. S-alkylated, derivatives of the oxidation-sensitive thiophenols in the cyclisation steps. Reductive cleavage of the macrobicyclic or macrotricyclic intermediates (6, 7, 11) afforded the free thiophenols (H4 8, H4 9, and H4 12) in preparative yields as their hydrochloride salts. The protected proligands can exist in two conformations, resembling the "cone" and "1,3-alternate" conformations found for the parent calix[4]arenes. The free macrocycles do not show conformational isomerism, but are readily oxidized forming intramolecular disulfide linkages. Preliminary complexation experiments show that these expanded mercaptocalixarenes can serve as supporting ligands for tetranuclear thiolato clusters.
More Related Videos
11:09Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation
Published on: August 1, 2018
09:45Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Related Concept Videos
Complexation Equilibria: The Chelate Effect
Complexation Equilibria: Factors Influencing Stability of Complexes
Complexometric Titration: Ligands
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
EDTA: Chemistry and Properties