Synthesis and characterization of mixed-metal complexes of Ag/Cu and W/Mo and a complex of Ag with heterocyclic thione ligands

Abstract

Reactions of AgI with salts of [WS(4)](2-) or [MoS(4)](2-) and with either imidazolidine-2-thione (Imt) or [1,3]diazepane-2-thione (Diap) give the complexes [WS(4)Ag(2)(Imt)(2)](n) and [MS(4)Ag(2)(Diap)(4)] [M = W or Mo]; in the case of Diap, corresponding Cu complexes can be obtained with CuCl instead of AgI. Decomposition of the Ag-Diap complexes during attempted recrystallization leads to the polymeric complex [AgI(Diap)](n). The monomeric mixed-metal Diap complexes contain edge-sharing WS(4) and AgS(4) tetrahedra, the Diap ligands being terminally bonded to Ag through sulfur. The mixed-metal W-Ag-Imt complex is a chain polymer with two different environments for the WS(4) unit and three different coordination environments for Ag, one of which is an unprecedented AgS(5) square-based pyramid; Imt ligands are terminally coordinated to Ag. [AgI(Diap)](n) has a complex polymeric chain structure with three different distorted tetrahedral environments for Ag, direct Ag-Ag bonding, both bridging and terminal I, and all Diap ligands bridging pairs of Ag atoms. All the crystal structures feature N-H[...]S or N-H[...]I hydrogen bonding. The complexes have also been characterised by infrared, UV-Vis and (1)H and (13)C NMR spectroscopy.

Synthesis, characterization and antibacterial activity of palladium(II) bromide complexes of thioamides; X-ray structure of [Pd(tetramethylthiourea)4]Br2

“…FT-IR spectra were recorded on a Thermo Nicolet Nexus 6700 USA. The 1 H and 13 C NMR spectra of the ligands and their complexes in DMSO-d 6 were obtained on a Bruker Avance 300 MHz NMR spectrometer operating at frequencies of 300.00 and 75.47 MHz, respectively, at 300 K. The spectral conditions were the following: 32 K data points, 1.822 s acquisition time, 2.00 s pulse delay and 6.00 ls pulse width. The 13 C chemical shifts were measured relative to TMS.…”

“…The chemical interest of thiones lies in the fact that they are potentially ambidentate ligands with sulfur and nitrogen atoms available for coordination, and they have binding sites relevant to those in living organisms [1][2][3][4][5][6]. In view of this, recently, a large number of studies have been devoted to the structural characterization of thione complexes of various metal ions and investigation into their biological properties .…”

Synthesis and spectroscopic characterization of cadmium(II) complexes of thiones and thiocyanate

“…Consequently, we have reported complexes of Cu(I), Ag(I), Au(I), Cd(II) and Hg(II) with a number of thiones such as imidazolidine-2-thione [8][9][10][11][12][13][14]. Although several cadmium(II) complexes of thiones have been prepared and characterized using NMR spectroscopy and X-ray crystallography [7,[14][15][16][17][18][19][20][21], no spectroscopic reports are available about the coordination behavior of thiones towards cadmium thiocyanate. As a part of our continuing interest in the structural chemistry of metal-sulfur interactions, we report here the synthesis of a number of cadmium(II) thiocyanate complexes of thiones and their characterization by IR, 1 H and 13 C NMR spectroscopy.…”

“…Chemical interest of thiones lies in the fact that they are potentially ambidentate or multi-functional donors with exocyclic S and heterocyclic N available for coordination; their biological interest arises from their structural analogy to thiolated nucleosides [2][3][4][5]7]. We have been investigating the coordination chemistry of 4C¼S ligands with d 10 metal ions in an attempt to assess their mode of binding and to study their physical properties [8][9][10][11][12][13][14].…”

Two polymorphs of tetraethylammonium [hydrogen tris(3,5-dimethylpyrazolyl)borato]di-μ2-sulfido-disulfido(η2-tetrasulfido)ditungsten(V) withZ′ = 1 and 2

“…In a long-term research project investigating mixed-metal cluster compounds with thiometallate cores (see, for example, Beheshti et al, 2007Beheshti et al, , 2008Beheshti et al, , 2011, we treated (Et 4 N)[Tp*WS 3 ] [Tp* À is hydrogen tris(3,5-dimethylpyrazolyl)borate, an established tripodal ligand] with AgI in acetonitrile solution. Elemental analysis and electronic and vibrational spectroscopy of the crude product indicated a successful synthesis of the intended product (Et 4 N)[Tp*WS 3 (AgI)] in a type of reaction we have used many times previously; however, attempted recrystallization from acetonitrile solution by vapour diffusion of diethyl ether led to decomposition and the unexpected isolation of the title complex, (Et 4 N)[Tp*W 2 S 2 -( 2 -S) 2 (S 4 )], (I), which was identified by crystal structure determination.…”