Syntheses, crystal structures, and genotoxic studies of cis-µ-1,2-peroxo dicobalt(III) complexes

Abstract

Two peroxo-bridged dinuclear Co(III) complexes, {[Co 2 (ea) 2 (Phen) 2 (O 2 )]·5.5H 2 O·2Cl} (1) and {[Co 2 (ea) 2 (Bipy) 2 (O 2 )]·2H 2 O·2NO 3 } (2) (Hea = ethanolamine, Phen = 1,10-phenanthroline, Bipy = 2,2′-bipyridine), are prepared by reaction of CoCl 2 ·6H 2 O or Co(NO 3 ) 2 ·6H 2 O with Hea in presence of an α-diimine (Phen or Bipy) under reflux. The complexes have been characterized by IR, NMR, TGA, cyclic voltammetric, PXRD and single crystal XRD techniques. Single crystal X-ray crystallographic investigations of 1 and 2 reveal that each Co(III) is coordinated by one deprotonated ethanolamine and an α-diimine chelate. The remaining coordination sites of the metal ions are satisfied by bridging peroxide (O 2 2-) in a cis-µ-1,2 manner. The distances [O-O = 1.487(6) (1) and 1.462(3) Å (2) and CoˑˑˑCo = 2.731(12) (1) and 2.7426(6) Å (2)] support the peroxo bridging in a cis manner in both complexes. The crystal lattice is consolidated via extensive H-bonding and π-π interactions to form a 3D supramolecular architecture. Thermal data are consistent with the proposed stoichiometry and presence of lattice water. The cyclic voltammetric studies of 1 indicate the presence of a quasi reversible redox couple (Co III -Co III /Co II -Co II ) in solution. Genotoxic studies are also performed on 1 to investigate the possible applications and side effects of the compounds in medicine.

Crystal structure of trans-bis[2-(1H-benzotriazol-1-yl)acetato-κO]bis(ethanolamine-κ2 N,O)copper(II)

“…The interaction of metal cations with MEA results in the formation of complexes in which MEA demonstrates monodentate (Hajji & Guerfel, 2016;Luo et al, 2012;Ren et al, 2014;Heinrich et al, 2012;Guzei et al, 2010a) and bidentate (Ibragimov et al, 2017;Seppä lä et al, 2013;Yeşilel et al, 2012;Xue et al, 2016;Ashurov et al, 2015) coordination modes. In some complexes, MEA has bridging properties (Shahid et al, 2015;Tudor et al, 2013;Schwarz et al, 2010;Maclaren et al, 2012;Seppä lä et al, 2012). In addition, there are metal complexes in which MEA molecules show non-coordinating behaviour (Wang et al, 2013;Lemmerer & Billing, 2010;Calderone et al, 2011;Yadav et al, 2015;Sutradhar et al, 2012;Liu et al, 2011).…”

Solutions of complex copper salts in low-transition-temperature mixture (LTTM)

“…25 There are a lot of interesting findings 7-10 related to the synthesis, structure and properties of MetILs with general formula MA 2 ·6L, where M = Fe(III), Cu(II), Mn(II), Zn(II); A = CF 3 SO 3 − = OTf (triflate anion), N(SO 2 CF 3 ) 2 − = NTf 2 (bis(trifluoromethylsulfonyl)imide), CH 3 (CH 2 )CH(C 2 H 5 )COO − = EHN (2-ethylhexanoate ion); L = DH 2 or EH (ethanolamine). It should be noted that deprotonation of the hydroxyl groups in the presence of amines usually yields metal alcoholates; 27,28 ethanolamine forms alcoholates under the same conditions as alcohols 29 and can form alcoholates even without addition of secondary and tertiary amines, yielding the ammonium tautomer. [7][8][9][10] In all MetILs the coordination number of the metal atom is six.…”

“…The crystal structure was solved and it appeared that: 9 (1) only two DH 2 of six are in the inner coordination sphere of Cu atom; (2) both DH 2 are chelating ligands forming coordination bonds via the N and O atoms; (3) one of the hydroxyl groups bound to Cu atom is deprotonated. It should be noted that deprotonation of the hydroxyl groups in the presence of amines usually yields metal alcoholates; 27,28 ethanolamine forms alcoholates under the same conditions as alcohols 29 and can form alcoholates even without addition of secondary and tertiary amines, yielding the ammonium tautomer. 30 And last (4), but not least: the Cu(II) coordination number is 4 + 2, which is typical of Cu(II) cations.…”