Document Type
Article
Article Version
Post-print
Publication Date
2-24-2014
Abstract
A series of tridentate pincer ligands, each possessing two sulfur and one nitrogen donor (SNS), based on bis-imidazolyl or bis-triazolyl salts were metallated with CuCl2 to give new tridentate SNS pincer copper(I) complexes [(SNS)Cu]+. These orange complexes exhibit a three-coordinate pseudo-trigonal-planar geometry in copper. During the formation of these copper(I) complexes, disproportionation is observed as the copper(II) salt precursor is converted into the Cu(I) [(SNS)Cu]+ cation and the [CuCl4]2– counteranion. The [(SNS)Cu]+ complexes were characterized with single crystal X-ray diffraction, electrospray mass spectrometry, EPR spectroscopy, attenuated total reflectance infrared spectroscopy, UV–Vis spectroscopy, cyclic voltammetry, and elemental analysis. The EPR spectra are consistent with anisotropic Cu(II) signals with four hyperfine splittings in the lower-field region (g||) and g values consistent with the presence of the tetrachlorocuprate. Various electronic transitions are apparent in the UV–Vis spectra of the complexes and originate in the copper-containing cations and anions. Density functional calculations support the nature of the SNS binding, allowing assignment of a number of features present in the UV–Vis and IR spectra and cyclic voltammograms of these complexes.
Publication Title
Journal of Coordination Chemistry
Repository Citation
Miecznikowski, John R.; Lynn, Matthew A.; Jasinski, Jerry P.; Reinheimer, Eric; Bak, Daniel; Pati, Mekhala; Butrick, Elizabeth E.; Drozdoski, Anne Elise R.; Archer, Kerry A.; Villa, Christine E.; Lemons, Elise G.; Powers, Erin; Siu, Margaret; Gomes, Camile D.; and Morio, Kaitlyn N., "Synthesis, Characterization, and Computational Study of Three-Coordinate SNS Copper(I) Complexes Based on Bis-Thione Ligand Precursors" (2014). Chemistry & Biochemistry Faculty Publications. 21.
https://digitalcommons.fairfield.edu/chemistry-facultypubs/21
Published Citation
Miecznikowski, John R.; Lynn, Matthew A; Jasinski, Jerry P.; Reinheimer, Eric; Bak, Daniel; Pati, Mekhala; Butrick, Elizabeth E.; Drozdoski, Anne Elise R.; Archer, Kerry A.; Villa, Christine E.; Lemons, Elise G.; Powers, Erin; Siu, Margaret; Gomes, Camile D.; Morio, Kaitlyn N. “Synthesis, Characterization, and Computational Study of Three-Coordinate SNS Copper(I) Complexes Based on Bis-Thione Ligand Precursors", Journal of Coordination Chemistry, 2014, 67(1), 29-44, Published online: 24 Feb 2014
DOI
10.1080/00958972.2014.883070
Peer Reviewed
Comments
Copyright 2014 Taylor & Francis - archived here with a 1 year embargo
"This is an Accepted Manuscript of an article published in Journal of Coordination Chemistry in 2014, available online: http://www.tandfonline.com/doi/abs/10.1080/00958972.2014.883070."