Hydroperoxo−Copper(II) Complex Stabilized by N₃S-Type Ligand Having a Phenyl Thioether

Bis(2‐methylbenzimidazolyl)amine‐Derived Copper Complexes and Their Antineoplastic Activity

“…Notably, the thiophene sulfur atom of 2 does not coordinate to the Cu Although we were not able to obtain X-ray quality crystals of the bis(perchlorate) Cu II complex of L 4 , substitution of one perchlorate for chloride allowed us to establish the solid-state structure of [CuL 4 Cl]ClO 4 (4-Cl), which is analogous to bis(2-methylpyridyl)aminothioether-Cu 2+ . [20] The nitrogen atoms coordinate in a meridional arrangement, as observed for 2 and 3 (Table 1). In contrast to the structure of 2, complex 4-Cl has a Cu1-S24 bond [2.749(1) Å] with the thioether arm in an apical position; this Cu-S distance is considerably longer than that reported for bis(2-methylpyridyl)aminothioether-Cu 2+ [2.604(1) Å].…”

“…In contrast to the structure of 2, complex 4-Cl has a Cu1-S24 bond [2.749(1) Å] with the thioether arm in an apical position; this Cu-S distance is considerably longer than that reported for bis(2-methylpyridyl)aminothioether-Cu 2+ [2.604(1) Å]. [20] The thioether ligand and the chloride ion in the fourth basal position [Cu1-Cl1 2.277(1) Å], define the square pyramidal gewww.eurjic.org …”

“…[19] In the case of 4, an additional band at λ = 451 nm (ε = 416 m -1 ) was assigned to the SǞCu ligand-to-metal charge-transfer band based on reports of a related bis(2-methylpyridyl)aminothioether-Cu 2+ system. [20] An analogous feature is absent in 2, indicating that the thiophene sulfur atom does not coordinate to the metal center in solution. ESI or FAB + mass spectra of all complexes were acquired in acetonitrile/ methanol in order to determine their behavior in solution.…”

Sulfur ligation in copper enzymes and models

“…Based on all these data, the authors suggest that the methionine ligand on the Cu B in DbM and PHM may be the site for the inactivation by hydrogen peroxide through oxidation into a sulfoxide group. The precursor of this sulfoxide is probably the Cu-OOH species, as described by Kodera et al [48]. As a matter of fact, these authors have prepared and characterized a hydroxoperoxo-copper(II) complex stabilized by a N3S-type ligand having a phenyl thioether donor.…”

“…To understand the possible involvement of the methionine ligand different copper(II) complexes with N3S-type ligand have been prepared in the literature [46][47][48]. A questioning model has been described by Réglier et al [46].…”