Copper(I) Complexes with Thiourea Derivatives as Ligands: Revealing Secrets of Their Bonding Scheme

Abstract

We have synthesized and characterized five copper(I) complexes with unsymmetrically substituted thiourea ligands. These include two coordination polymers, [Cu(S tu NH)Br] n and [Cu(S tu(Py) NH)Br] n , two dinuclear complexes, [Cu 2 (S tu NH) 4 Br 2 ] and [Cu 2 (S tu(Py) NH) 2 Br 2 (MeCN) 2 ], and one hexanuclear complex, [Cu 6 (S tu N) 6 ]. The Cu atoms of the coordination polymers are connected through alternating thione and bromide bridges and the dimeric structures through thione bridges. The thionebridged structures show similarities with the biologically highly [a] 1266 Scheme 2. Reaction scheme leading to the copper(I) complexes C1-C5. The ratios in parentheses refer to ligand/metal ratio.

Single metal isotherm study of the ion exchange removal of Cu(II), Fe(II), Pb(II) and Zn(II) from synthetic acetic acid leachate

“…The argument for a redox reaction between copper and thiourea can be further justified by the calculation of high sorption free energies (17kJ • mol −1 ), alluding to a chemisorption process, with the better fit to the Temkin isotherm (over Langmuir and Freundlich) alluding to a heterogeneous binding mechanism, supported by the multitude of species formed by the redox reaction between aqueous thiourea and copper(II) [56,57].…”

Aqueous-Based Binary Sulfide Nanoparticle Inks for Cu2ZnSnS4 Thin Films Stabilized with Tin(IV) Chalcogenide Complexes

“…Instead, a dissociative process can be used to make the tin chalcogenide complex as per the method of Krebs involving dissolution of tin(IV) sulfide into aqueous ammonium sulfide solution [25] adopted for CZTS film fabrication by Ritchie et al [29]. In both of these CZTS aqueous nanoink works [28,29], thiourea was used as a supplementary complexing-stabilizing agent [30,31,32] for the soluble copper and zinc salts. Given that thiourea is classified as a likely human carcinogen [33], cleaner processing routes must be pursued.…”

Synthesis, characterization and crystal structure of platinum(II) complexes with thiourea derivative ligands

“…For example N-(alkyl/aryl)-N'-acylthiourea and N-di(alkyl/aryl)-N'-acylthiourea derivatives which have oxygen, nitrogen and sulphur donor atoms, exhibit prevalent coordination modes. Organic ligands that have thiourea moiety are able to bind metal ions in several ways, like: (i) acting as monodentate ligands through sulphur atom in mononuclear complexes [1-4] (ii) binding to metal ions forming S-bridges in dinuclear complexes [4][5][6][7][8] or (iii) chelating sulphur and nitrogen atoms [4][5][6][8][9][10][11][12][13][14][15][16] Thiourea derivatives as a ligand have a large dipole moment and these ligands can also form extensive network of hydrogen bonds due to their unique structures. For example in 3-monosubstituted arylthioureas [17][18][19], the carbonyl group and the proton on the nitrogen attach in a strong hydrogen bond interaction which unite into a planar six-membered ring structure forming an "S" shaped conformation of the C=O and C=S groups [20,21].…”