Anion-assisted self-assembly of chlorodiorganotin(IV) dithiocarbamate derived from naphthylimide

Two new chlorodiorganotin(IV) dithiocarbamate complexes with general formula ((R2SnCl)dtc) (dtc = (RRNCS2-)-R-1-N-2, R-1 = Bn. R-2 = naphtylimide; 3, R = n-Bu; 4, R - n. Ph) have been prepared from sodium N(2-(benzylamino)ethylinaphthalene-1,8-dicarboximide dithiocarbamate 2. The bis-dithiocarbamete 3d (R2Sn(dtc)(2), R = n-Bu) was obtained as the thermodynamic product during the titration process (vide infra). All compounds were characterized by mass spectrometry, IR, H-1 and C-13 NMR spectroscopy. The chlorodiorganotin(IV) dithiocarbamate complexes 3-4 also were characterized by Sn-119 NMR spectroscopy and single crystal X-ray diffraction analysis. The crystallographic study of these complexes showed the existence of C-H...pi, S...pi and pi...pi intramolecular interactions, indicating that the naphthylimide aromatic fragment stabilized the complexes. Complexes 3 and 4 were studied as host for anions (CH3CO2-, F-, H2PO4-) in CDCl3 by UV-Vis and Sn-119 NMR spectrometric titration. The tested anions cause the displacement of the chloride ligand of the metallic centre. The excess of F- or H2PO4 induce the self-assembly of diorganotin(IV) dithiocarbamate to bis-dithiocarbamates R2Sn(dtc)(2) (3d) instead of the breaking of the S-Sn covalent bond. Quantum mechanical calculations at DFf level (B3LYP/def2-TZVP) were performed to obtain the thermodynamic parameters of the reactions involved in the anion addition to the complexes. (C) 2018 Elsevier Ltd. All rights reserved.