Cadmium complexes of thiones. Part II. A synthetic, solution, and solid-state MAS Cd-111/113 NMR study of cadmium complexes of 1,3-thiazolidine-2-thione, and the structures of [tetrakis(1,3-thiazolidine-2-thione)cadmium] trifluoromethanesulfonate ([C

摘要

Treatment of Cd(O3SCF3)(2) with the stoichiometric quantity of 1,3-thiazolidine-2-thione (tztH) allows isolation of [Cd(tztH)(4)](O3SCF3)(2) (1). When tztH:Cd greater than or equal to 2 the reaction of Cd(NO3)(2). 4H(2)O with tztH leads to [Cd(tztH)(4)][Cd(O2NO)(4)] (2). The structures of both 1 and 2 have been determined by single crystal X-ray analysis. Colourless crystals of 1 are orthorhombic, space group Fdd2, with eight molecules per unit cell (Z = 8) of dimensions a = 20.139(3), b = 23.332(5), c = 14.214(3) Angstrom. Those of 2 are tetragonal, space group I (4) over bar, with four molecules per unit cell (Z = 4) of dimensions a = 13.8853(11), c = 8.077(2) Angstrom. The discrete homoleptic cation [Cd(tztH)(4)](2+) is characterized for the first time in 1 and 2. The cations are of point group symmetry C-2 and S-4 in 1 and 2, respectively. In both cases the ligands are S-bound, and the CdS4 kernel is a squashed tetrahedron. In 2, the eight-coordinate anion [Cd(O2NO)(4)](2) is characterized for the second time. Cd-113 CP MAS NMR data are reported for solid 1 and 2, and also for solids produced by fusing Cd(NO3)(2). 4H(2)O with different molar ratios amounts of tztH, and by fusing Cd(O3SCF3)(2) with six mol equivalents of tztH. In the Cd(NO3)(2)4H(2)O:tztH mixtures, species identified include unreacted cadmium salt 2 ([Cd(tztH)(4)](NO3)(2)) and possibly Cd(tztH)(3)(NO3)(2). [Cd(tztH)(4)](NO3)(2) becomes the major species only when a significant excess of tztH is used. In the mixtures with tztH:Cd > 4, neither Cd(NO3)(2). 4H(2)O nor Cd(O3SCF3)(2) form complexes containing more than four tztH ligands. Reduced-temperature Cd-111 NMR data are reported for Cd(ClO4)(2.)6H(2)O:tztH mixtures in MeOH. Species identified are Cd(tztH)(w)(2+)(solv) (w = 0-3). [References: 44]