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Updated: May 8, 2026
14:44
Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
Dicopper(I) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand
Laurent Sévery1,2, T Alexander Wheeler1,2, Amelie Nicolay1
1Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720-1460, USA. tdtilley@berkeley.edu.
Dalton Transactions (Cambridge, England : 2003)
|February 27, 2025
Summary
A novel dinucleating ligand, 1,8-naphthyridine-2,7-bis(2,6-diisopropylphenyl)carboxamide (NBDA), was synthesized and used to create unique dicopper(I) complexes. These complexes exhibit weaker copper-copper interactions and ionic bonding, influencing their structural and electrochemical properties.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- The synthesis and characterization of novel dinucleating ligands are crucial for developing new metal complexes with tailored properties.
- 1,8-naphthyridine derivatives have shown promise in coordinating metal ions for various applications.
Purpose of the Study:
- To synthesize and characterize novel dicopper(I) complexes using the dinucleating ligand 1,8-naphthyridine-2,7-bis(2,6-diisopropylphenyl)carboxamide (NBDA).
- To investigate the structural, spectroscopic, electrochemical, and computational properties of these dicopper(I) complexes.
Main Methods:
- Palladium-catalyzed aminocarbonylation for ligand synthesis.
- Reaction of the ligand with mesitylcopper(I) to form anionic and neutral dicopper(I) complexes.
- Characterization using NMR, IR spectroscopy, and single-crystal X-ray diffraction.
- Electrochemical studies via cyclic voltammetry and DFT calculations.
Main Results:
- Successful synthesis of anionic [Bu4N][Cu2(NBDA)(μ-X)] (X = Cl, N3) and neutral [Cu2(NBDA)(CNXyl)2] complexes.
- X-ray diffraction revealed intermetallic separations over 3 Å due to strong copper-amide nitrogen coordination.
- Electrochemical analysis showed reversible ligand-based reduction between -1.65 and -2.0 V vs. Fc/Fc+.
- DFT calculations indicated more ionic bonding and weaker Cu-Cu interactions compared to related ligands.
Conclusions:
- The NBDA ligand facilitates the formation of dicopper(I) complexes with distinct structural and electronic properties.
- Strong coordination to amide nitrogen donors influences the Cu-Cu distance and bonding character.
- These findings contribute to the understanding of metal-ligand interactions in polynuclear complexes.
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