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Expanded Mercaptocalixarenes: A New Kind of Macrocyclic Ligands for Stabilization of Polynuclear Thiolate Clusters.

Authors :
Schleife, Frederik
Bonnot, Clément
Chambron, Jean‐Claude
Börner, Martin
Kersting, Berthold
Source :
Chemistry - A European Journal; 4/12/2022, Vol. 28 Issue 21, p1-12, 12p
Publication Year :
2022

Abstract

The syntheses and properties of expanded 4‐tert‐butyl‐mercaptocalix[4]arenes, in which the methylene linkers are replaced by −CH2NRCH2− or −CH2NRCH2− and −CH2NRCH2CH2CH2NRCH2− 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 (H48, H49, and H412) 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. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
09476539
Volume :
28
Issue :
21
Database :
Complementary Index
Journal :
Chemistry - A European Journal
Publication Type :
Academic Journal
Accession number :
156278103
Full Text :
https://doi.org/10.1002/chem.202104255