Three new Ag(I) thiosaccharinate complexes: syn-thesis, structural studies, spectral characterization and theoretical analysis

DORN, VIVIANA; ROBERT A. BURROW; MARIANA DENNEHY; GIANCARLO Z. BELMONTE

INORGANICA CHIMICA ACTA

ELSEVIER SCIENCE SA

Lugar: Amsterdam; Año: 2016 vol. 450 p. 39 - 49

0020-1693

Three silver thiosaccharinate complexes, two of them with diverse coordination geometries controlled by the ancillary nitrogen donor ligands are presented. The dinuclear silver thiosaccharinate complex, catena-poly-[Ag2(tsac)2]?C3H7NO (1?DMF), (thiosaccharinate = thiosaccharinate anion, DMF = dimethylformamide) in the crystalline state is a one dimen-sional coordination polymer bridged by the thiosaccharinate ligand with a very short silver-silver distance, 2.8930(16) Å. The biquinoline silver(I) thiosaccharinate, [Ag(tsac)(2,2′‑bquin)]?CH3CN (2?CH3CN), (bquin = 2,2′-biquinoline) in the crystalline state consists of a mononuclear neutral unit solvated with an acetonitrile molecule. The double complex salt, [Ag(2,4,6-coll)2][Ag(tsac)2] (3), (2,4,6-coll = 2,4,6-collidine) possesses a very unusual arrangement for a silver thiosaccharinate, one similar to an ionic silver-pyridine based structure. The complex cation is formed two 2,4,6-trimethylpyridine molecules coordinated to the silver atom with approximate tetrahedral geometry while the complex anion is composed of two thiosaccharinate anions coordinated to the silver atom in a planar arrangement. Their syntheses, full characterizations and crystal structures are described. The structures of these newly synthesized silver(I) thiosaccharinate complexes have been optimized and their structural parameters have been calculated at the B3LYP/6-31G(2d,p)/LANL2DZ level of theory. The 13C NMR chemical shifts for the DMSO solution species of (2) & (3) were calculated using DFT/EPR-III/DZP first principles calculations with B3LYP, OLYP, OPBE, HCTH93 functionals.