Synthesis, characterization, and computational study of three-coordinate SNS-copper(I) complexes based on bis-thione precursors

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 CuCl 2 to give new tridentate SNS pincer copper(I) complexes [(SNS)Cu] + . These orange complexes exhibit a three-coordinate pseudo-trig...

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Bibliographic Details
Published in:Journal of coordination chemistry 2014-01, Vol.67 (1), p.29-44
Main Authors: Miecznikowski, John R., Lynn, Matthew A., Jasinski, Jerry P., Reinheimer, Eric, Bak, Daniel W., 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.
Format: Article
Language:English
Subjects:
Anisotropy
Cations
Copper
Cyclic voltammetry
Density
Density functional theory calculations
Electronics
Electrons
EPR spectroscopy
Precursors
SNS Cu pincer complexes
SNS pincer ligand
Spectra
Spectroscopy
Sulfur
Voltammetry
X-ray crystallography
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Summary: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 CuCl 2 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 [CuCl 4 ] 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.
ISSN:0095-8972
1029-0389
DOI:10.1080/00958972.2014.883070