Effect of weak sulfur...C(π) interactions, and hydrogen bonds in supramolecular association of chlorodiphenyltin(IV) dithiocarbamate complexes: Study of their stability in solution

摘要

Five new chlorodiorganotin(IV) complexes derived from dithiocarbamate ligands have been prepared and structurally characterized. The complexes 1-5 with the general formula {(Ph _2SnCl)dtc} (dtc = R _1R _2NCS _2 ~-; 1, R _1 = Bn, R _2 = 9-anthrylmethyl; 2, R _1 = Bn, R _2 = 9-phenanthrylmethyl; 3, R _1 = Bn, R _2 = 1-pyrenylmethyl; 4, R _1 = 1-naphthylmethyl, R _2 = 1-pyrenylmethyl; 5, R _1 = R _2 = 1-pyrenylmethyl) have been obtained from Ph _2SnCl _2 and the sodium dithiocarbamate salts of benzyl(9-anthrylmethyl) amine, benzyl(9-phenanthrylmethyl)amine, benzyl(1-pyrenylmethyl)amine, 1-naphthylmethyl(1-pyrenylmethyl)amine and di(1-pyrenylmethyl)amine. Compounds 1-5 have been analyzed as far as possible by elemental analysis, FAB ~+ mass spectrometry, IR, UV-Vis, fluorescence and NMR (~1H, ~(13)C, ~(119)Sn) spectroscopy, and single-crystal X-ray diffraction analysis (1-3). The solid-state and solution studies showed that the dtc ligands are coordinated to the tin atoms in the anisobidentate manner. In all cases the metal centers are five-coordinate. The coordination geometry is intermediate between square-pyramidal and trigonal-bipyramidal coordination polyhedra with τ-values in the range of 0.49-0.55. The crystal structures show the presence of C-H?Cl, C-H?S, C-H?π, offset π-π and S?π contacts. The stability of the (Ph _2SnCl)dtc complexes in the presence of the acetate anion has been examined in acetonitrile solutions. For all of these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dtc) by the acetate anion was observed. The lability, as well as their intrinsic fluorescent properties of the polyaromatic moieties in these (Ph _2SnCl)dtc compounds make them interesting candidates to detect the presence of O-donor anions at very low concentrations by displacement of the metal-coordinated dtc.