Reaction of Bis(N,N-dimethylthiocarbamoyl) Sulfide with Copper(II) Halides and the Crystal and Molecular Structures of Halogeno(bis(N,N-dimethylthiocarbamoyl) sulfido)copper(I) Complexes

Abstract

Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides ( halide) Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S 2 CuX units. The Cl derivative (1) is an S-bridged dimer (C 6 H 14 -ClCuN 2 OS 3 , monoclinic, P2 1 /c (No. 14), Z ) 4, a ) 9.525(8) Å, b ) 13.022(10) Å, c ) 10.835(7) Å), while the Br analogue (2) features a polymeric network of S 2 CuBr units, also bridged by S atoms (C 6 H 12 BrCuN 2 S 3 , orthorhombic, P2 1 2 1 2 1 (No.19), Z ) 4, a ) 7.043(2) Å, b ) 9.442(3) Å, c ) 17.889(4) Å). The iodo compound (3) exists as a halogen-bridged dimer (C 6 H 12 CuIN 2 S 3, monoclinic, P2 1 /m (No. 11), Z ) 4, a ) 9.570(1) Å, b ) 10.578(1) Å, c ) 12.422(1) Å). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1 H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.

Neutral Complexes of Silver Halides and Tetramethylthiuram Monosulfides

“…The differences observed between IR and Raman spectra are significant enough that adherence to the rule of mutual exclusion is still observed. This situation is similar to the one observed in the case of CuMe4tmsX @=Cl and I) [3]. However, an alternative structure based on oligomeric chains of halogen-bridged -.…”

“…For the latter compounds, a similar halogen-dibridged structure was anticipated on the basis of vibrational spectroscopy for the Me-substituted derivatives, while the evidence for the Et series pointed at monomeric tricoordinate formulations [lo]. Single crystal X-ray diffraction studies fully confirmed these expectations [3,4].…”

Synthesis, Structural and Optical Properties of TOPO and HDA Capped Cadmium Sulphide Nanocrystals, and the Effect of Capping Ligand Concentration

“…The band present in the 930 cm −1 range is attributed to the prevailing contribution of C⋅ ⋅ ⋅ S. Vibrations in these ranges have been used effectively in differentiating between the bonding formats of the dithiocarbamate ligand to the metal ion. The presence of only one strong band indicates symmetrical bidentate coordination of the dithio ligand, whereas a doublet is expected in the case of unsymmetrical monodentate coordination [28]. Medium to low bands at 2962-2973 cm −1 are attributed to the asymmetric ](allylic)C-H cm −1 stretching vibration, while bands at 3054-3075 cm −1 are due to ](allylic)=C-H.…”

“…An increase in vibrational frequency of about 15 cm −1 was observed upon complexation which could be due to the movement of the electron cloud of the -NCSS group after coordination to the metal center [27]. The result is a stronger metal-sulphur (M-S) bond and more stable chelates [28]. The band present in the 930 cm −1 range is attributed to the prevailing contribution of C⋅ ⋅ ⋅ S. Vibrations in these ranges have been used effectively in differentiating between the bonding formats of the dithiocarbamate ligand to the metal ion.…”

Syntheses, properties, crystal and molecular structure of a novel neutral pentanuclear copper(I) iodide species. Copper(I) complexes with tetraethylthiuram monosulfide ‡

“…All these involve anionic complexes. Thus Baumgartner 1 described the structure of the tetraphenylphosphonium salt of [Cu 5 (SMe) 7 ] 2Ϫ , a species isostructural to [Cu 5 (SPh) 4 Relevant aspects of the ligating properties of thiuram disulfides R 2 NC(S)S᎐SC(S)NR 2 (R = alkyl) have been reviewed in a previous paper, 5 where the significance of these compounds in the field of agriculture and medicine has been remarked upon. Particularly striking has been the application of these materials as inhibitors of human immunodeficiency viral infections such as AIDS.…”