629615-88-9Relevant academic research and scientific papers
Evaluation of the influence of a thioether substituent on the solid state and solution properties of N3S-ligated copper(II) complexes
Tubbs, Kyle J.,Fuller, Amy L.,Bennett, Brian,Arif, Atta M.,Makowska-Grzyska, Magdalena M.,Berreau, Lisa M.
, p. 3111 - 3116 (2003)
Admixture of a N3S(thioether) ligand having two internal hydrogen bond donors (pbnpa: N-2-(phenylthio)ethylN,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. The Royal Society of Chemistry 2003.
