Evaluation of the Influence of a Thioether Substituent on the Solid State and Solution Properties of N₃S-ligated Copper(II) Complexes

Authors

Kyle J. Tubbs, Utah State University
Amy L. Fuller, Utah State University
Brian Bennett, Marquette UniversityFollow
Atta M. Arif, University of UtahFollow
Magdalena Makowska-Grzyska, University of Chicago
Lisa M. Berreau, Utah State University

Document Type

Article

Language

eng

Format of Original

6 p.

Publication Date

2003

Publisher

The Royal Society of Chemistry

Source Publication

Dalton Transactions

Source ISSN

1477-9226

Original Item ID

doi: 10.1039/B304846B

Abstract

Admixture of a N₃S(thioether) ligand having two internal hydrogen bond donors (pbnpa: N-2-(phenylthio)ethyl-N,N-bis-((6-neopentylamino-2-pyridyl)methyl)amine; ebnpa: N-2-(ethylthio)ethyl-N,N-bis-((6-neopentylamino-2-pyridyl)methyl)amine) with equimolar amounts of Cu(ClO₄)₂·6H₂O and NaX (X = Cl⁻, NCO⁻, or N₃⁻) in CH₃OH/H₂O yielded the mononuclear Cu(II) derivatives [(pbnpa)Cu–Cl]ClO₄ (1), [(ebnpa)Cu–Cl]ClO₄ (2), [(pbnpa)Cu–NCO]ClO₄ (3), [(ebnpa)Cu–NCO]ClO₄ (4), [(pbnpa)Cu–N₃]ClO₄ (5), and [(ebnpa)Cu–N₃]ClO₄ (6). Each complex was characterized by FTIR, UV-VIS, EPR, and elemental analysis. Complexes 1, 2, 3 and 6 were characterized by X-ray crystallography. The structural studies revealed that [(pbnpa)Cu–X]ClO₄ derivatives (1, 3) exhibit a distorted square pyramidal type geometry, whereas [(ebnpa)Cu–X]ClO₄ complexes (2, 6) may be classified as distorted trigonal bipyramidal. EPR studies in CH₃OH/CH₃CN solution revealed that 1–6 exhibit an axial type spectrum with g_∥ > g_⊥ > 2.0 and A_∥ = 15–17 mT, consistent with a square pyramidal based geometry for the Cu(II) center in each complex. A second species detected in the EPR spectra of 2 and 6 has a smaller A_∥ value, consistent with greater spin delocalization on to sulfur, and likely results from geometric distortion of the [(ebnpa)Cu(II)–X]⁺ ions present in 2 and 6.

Comments

Accepted version. Dalton Transactions, No. 15 (2003): 3111-3116. DOI. © 2003 Royal Society of Chemistry. Used with permission.

Brian Bennett was affiliated with the Medical College of Wisconsin at the time of publication.

Recommended Citation

Tubbs, Kyle J.; Fuller, Amy L.; Bennett, Brian; Arif, Atta M.; Makowska-Grzyska, Magdalena; and Berreau, Lisa M., "Evaluation of the Influence of a Thioether Substituent on the Solid State and Solution Properties of N₃S-ligated Copper(II) Complexes" (2003). Physics Faculty Research and Publications. 83.
https://epublications.marquette.edu/physics_fac/83