Synthesis and structural studies of copper(ii) complex with N2S2 based N-substituted pendant phosphonic acid arms

The synthesis of a heteromacrocyclic bifunctional chelator with phosphonic acid pendent arms is presented along copper(ii) complexation. Ligand N2S2-POH featuring N,N′-bis-substituted phosphonate pendent arms was isolated in respectable yields, characterized, and chelated to copper(ii). Implementati...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2020-03, Vol.49 (11), p.3545-3552
Main Authors: Taschner, Ian S, Aubuchon, Ethan, Schrage, Briana R, Ziegler, Christopher J, Art van der Est
Format: Article
Language:English
Subjects:
Acids
Chelates
Coordination compounds
Copper
Copper compounds
Crystallography
Hydronium ions
Ion concentration
NMR
Nuclear magnetic resonance
Phosphonates
Phosphonic acids
Room temperature
Substitutes
Synthesis
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Summary:The synthesis of a heteromacrocyclic bifunctional chelator with phosphonic acid pendent arms is presented along copper(ii) complexation. Ligand N2S2-POH featuring N,N′-bis-substituted phosphonate pendent arms was isolated in respectable yields, characterized, and chelated to copper(ii). Implementation of both Moedritzer–Irani and Kabachnik–Fields conditions using aza–thia macrocycle 1,8-dithia-4,11-diazacyclotetradecane afforded 1,8-dithia-4,11-diazacyclotetradecane-4,11-diyl-bis-(methylene)-bis-(phosphonic acid) (N2S2-POH). Kinetic NMR studies provided four acid dissociation constants with respect to hydronium ion concentration. Benesi–Hildebrand binding experiment provided a conditional formation constant of 2.8 × 104 M−1. Heteromacrocycle N2S2-POH readily formed an encapsulated copper(ii) chelate at room temperature, which was examined through EPR analysis.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt04869c