Structural Rearrangement in Cyclic Cu(II) Pyridyltriazole Complexes: Oxidation of Dabco to Oxalate and CO<sub>2</sub> Conversion to Carbonate

Structural Rearrangement in Cyclic Cu(II) Pyridyltriazole Complexes: Oxidation of Dabco to Oxalate and CO<sub>2</sub> Conversion to Carbonate

Structural rearrangements in metal–organic supramolecules constructed from the coordination of Cu(II) with <i>m</i>-xpt (<i>m</i>-xylylenebis(pyridyltriazole)) are investigated upon their interaction with 1,4-diazabicyclo[2.2.2]octane (dabco) and carbon dioxide-enriched air....

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Bibliographic Details
Main Authors: Uttam R. Pokharel, Frank R. Fronczek, Andrew W. Maverick
Format: Article
Language:English
Published: MDPI AG 2025-03-01
Series:Molecules
Subjects:
rearrangements
metal–organic supramolecules
dabco
carbonate and oxalate bridges
copper(II) complexes
pyridyltriazole
Online Access:https://www.mdpi.com/1420-3049/30/7/1430
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Summary:Structural rearrangements in metal–organic supramolecules constructed from the coordination of Cu(II) with <i>m</i>-xpt (<i>m</i>-xylylenebis(pyridyltriazole)) are investigated upon their interaction with 1,4-diazabicyclo[2.2.2]octane (dabco) and carbon dioxide-enriched air. The binuclear [Cu<sub>2</sub>(<i>m</i>-xpt)<sub>2</sub>]<sup>4+</sup> complexes react with dabco to produce a carbonate-bridged trinuclear complex, [Cu<sub>3</sub>(<i>m</i>-xpt)<sub>3</sub>(µ-CO<sub>3</sub>)]<sup>4+</sup>, and an oxalate-bridged binuclear complex, [Cu<sub>2</sub>(<i>m</i>-xpt)<sub>2</sub>(µ-C<sub>2</sub>O<sub>4</sub>)]<sup>2+</sup>, where carbonate and oxalate likely originate from CO<sub>2</sub> and dabco, respectively. The trinuclear complex reassembles the original dimer upon the removal of the carbonate ion. Similarly, polymeric [Cu(<i>o</i>-xpt)(PF<sub>6</sub>)]<sub>n</sub>, formed from Cu(I) and <i>o</i>-xpt (<i>o</i>-xylylenebis(pyridyltriazole)) coordination, undergoes oxidation in CO<sub>2</sub>-enriched air to yield a tetranuclear Cu(II) complex, Cu<sub>4</sub>(<i>o</i>-xpt)<sub>3</sub>(μ<sub>4</sub>-CO<sub>3</sub>)(μ<sub>2</sub>-OH)(μ<sub>2</sub>-OCOCH<sub>3</sub>)<sup>4+</sup>. The reaction progress is monitored by UV-Vis spectroscopy, and the major products are characterized by single-crystal X-ray diffraction.
ISSN:1420-3049

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