Dicopper(I) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand

Sévery, Laurent; Wheeler, T. Alexander; Nicolay, Amelie; Teat, Simon J.; Tilley, T. Don

doi:10.1039/d5dt00034c

Dicopper(I) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand

Journal Article · Fri Feb 21 00:00:00 EST 2025 · Dalton Transactions

DOI:https://doi.org/10.1039/d5dt00034c· OSTI ID:2584840

^[1]; Wheeler, T. Alexander ^[1]; Nicolay, Amelie ^[2]; ^[3]; ^[1]

University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

The dinucleating ligand, 1,8-naphthyridine-2,7-bis(2,6-diisopropylphenyl)carboxamide (NBDA), was synthesized by palladium-catalyzed aminocarbonylation. This ligand was treated with two equivalents of mesitylcopper(I) in the presence of [ⁿBu₄N]X (X = Cl, N₃) to give the anionic complexes [ⁿBu₄N][Cu₂(NBDA)(μ-Cl)] and [ⁿBu₄N][Cu₂(NBDA)(μ-N₃)]. Treatment of H₂NBDA with mesitylcopper(I) and two equivalents of xylyl isocyanide led to the formation of a charge-neutral dicopper(I) complex, [Cu₂(NBDA)(CNXyl)₂], displaying two isocyanide ligands, each terminally bound to one of the copper atoms. The complexes were characterized by NMR and IR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Electrochemical characterization of the complexes using cyclic voltammetry revealed a reversible ligand-based reduction between −1.65 and −2.0 V vs. Fc/Fc⁺. DFT calculations suggest a more ionic bonding character and weaker Cu–Cu interactions in the NBDA complexes compared to those with other 1,8-naphthyridine-based ligands. In conclusion, this is congruent with intermetallic separations of over 3 Å induced by relatively strong coordination of the copper atoms to the amide nitrogen donor atoms observed in the solid state molecular structures.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Swiss National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2584840

Alternate ID(s):: OSTI ID: 2524621

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 20 Vol. 54; ISSN 1477-9226; ISSN 1477-9234

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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