A New Thioether‐Based (N₂S₂)Copper(II/I) Complex Exhibiting a High Redox Potential

Abstract

(2) were synthesized and characterized by X-ray crystallography. The Cu−S bonds are unusually shortened in 1 and elongated for the axial thioether in 2.

Redox-Innocent Metal-Assisted Cleavage of S–S Bond in a Disulfide-Containing Ligand

“…The mean Cu−N distances are 2.007 and 2.000 Å for Cu1 and Cu2, respectively, in agreement with usual Cu II −N bond length values. 29,65,66 The O1−S1 and O2−S1 distances are different (1.533(2) and 1.494(2) Å, respectively), indicating single and double bond characters as already reported for other Cu II −sulfinato complexes. 35,38,39,67 Finally, the Cu1−Cu2 distance in 2 of 6.380 Å is longer than those in the recent report on sulfinato-bridged dicopper(II) compounds (3.63 and 3.47 Å) by Bouwman and colleagues.…”

Copper‐Azide‐Thioarylazoimidazoles – Structure, Spectra, Redox Properties, Magnetism and Theoretical Interpretation

“…Some of the transitions are new ( Table 2, Figure 3) in the complexes: these are characteristic of copper(II) azoheterocycles [16,19,22] and are the MLCT transitions involving dπ(Cu)Ǟπ*(arylazoheterocycle). By comparing them with values for copper(II)-1-alkyl-2-(arylazo)-imidazoles, [11][12][13]16] copper(II)-2(arylazo)pyridine, [19] copper(II)-pyridylthioazophenolates [22] and other pyridylthioethers, [23] we can assign the transitions at approximately 410 nm to the MLCT [dπ(Cu)Ǟπ*(azoimidazole)] band, and the absorption at approximately 740 nm is undoubtedly a d-d transition. [24] The visible ranges of the spectra of copper(I) complexes (3,4) show similar metal-to-ligand chargetransfer (MLCT) transitions at 710-765 nm and 410- complexes when bonded with conjugated organic chromophores.…”

Sulfur ligation in copper enzymes and models

“…From N 2 (StBu) 2 ligand (2-pyridylmethyl)bis(2-tertbutyl-thiobenzyl)amine the corresponding [Cu(I)(N 2 (StBu) 2 ] CF 3 SO 3 (1) and [Cu(II)(N 2 (StBu) 2 )(H 2 O)(C F 3 SO 3 )] CF 3 SO 3 (2) complexes were synthesized and characterized by X-ray crystallography [41] (Fig. 5).…”

“…(a) The two reversibly interconvertible redox states of a copper complex with two thioether ligands, (b) the corresponding X-ray structures for 1 1+ and 2 1+[41].…”