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 ([Cd(C3H5NS2)(4)](CF3SO3)(2)) and [tetrakis(1,3-thiazolidine-2-thione)cadmium][tetrakis(nitrato-O,O ')cadmate] ([Cd(C3H5NS2)(4)][Cd(O2NO)(4)])

Citation
U. Rajalingam et al., 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 ([Cd(C3H5NS2)(4)](CF3SO3)(2)) and [tetrakis(1,3-thiazolidine-2-thione)cadmium][tetrakis(nitrato-O,O ')cadmate] ([Cd(C3H5NS2)(4)][Cd(O2NO)(4)]), CAN J CHEM, 79(9), 2001, pp. 1330-1337
Citations number
44
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
ISSN journal
0008-4042 → ACNP
Volume
79
Issue
9
Year of publication
2001
Pages
1330 - 1337
Database
ISI
SICI code
0008-4042(200109)79:9<1330:CCOTPI>2.0.ZU;2-7
Abstract
Treatment of Cd(O3SCF3)(2) with the stoichiometric quantity of 1,3-thiazoli dine-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 crysta ls of 1 are orthorhombic, space group Fdd2, with eight molecules per unit c ell (Z = 8) of dimensions a = 20.139(3), b = 23.332(5), c = 14.214(3) Angst rom. Those of 2 are tetragonal, space group I (4) over bar, with four molec ules per unit cell (Z = 4) of dimensions a = 13.8853(11), c = 8.077(2) Angs trom. 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 t he 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 da ta are reported for solid 1 and 2, and also for solids produced by fusing C d(NO3)(2). 4H(2)O with different molar ratios amounts of tztH, and by fusin g Cd(O3SCF3)(2) with six mol equivalents of tztH. In the Cd(NO3)(2)4H(2)O:t ztH 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) beco mes the major species only when a significant excess of tztH is used. In th e mixtures with tztH:Cd > 4, neither Cd(NO3)(2). 4H(2)O nor Cd(O3SCF3)(2) f orm complexes containing more than four tztH ligands. Reduced-temperature C d-111 NMR data are reported for Cd(ClO4)(2.)6H(2)O:tztH mixtures in MeOH. S pecies identified are Cd(tztH)(w)(2+)(solv) (w = 0-3).