Dithiocarbamates of transition group elements in “unusual” oxidation states

A number of dithiocarbamate derivatives Ph2Te[S2CNR2I2, where R = Me, Et, and Ph2TeC1[S2CNR2], where R = Me, Et, i-Pr, have been prepared and characterized initially by analysis and vibrational spectroscopy. Three crystal structures have been completed that allow for comparisons of the effect of the change in the nature of R and of the presence of a chlorine atom. The dithiocarbamate groups are monodentate (or anisobidentate) and the geometry about tellurium is consistently that of a distorted sawhorse structure. Examples of both inter-and intra-molecular Te.. . S interactions are observed as well as an intermolecular

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Preparation and characterization of diphenylbis(N,N-dialkyldithiocarbamato)tellurium (IV) and chlorodiphenyl(N,N-dialkyldithiocarbamato)tellurium(IV). Crystal structures of Ph₂Te[S₂CNMe₂]₂, Ph₂TeCl[S₂CNEt₂], and Ph₂TeCl[S₂CN(i-Pr)₂]

Bailey¹,

Drake²,

Sarkar³

et al. 1989

“…The redox behaviour of dithiocarbamates and their metal complexes has been extensively studied (4)(5)(6)(7)(8) and is noteworthy for the stabilization of unusually high oxidation states of transition metals in metal dithiocarbamate complexes. In contrast, the electrochemistry of dithiocarboxylates has barely been investigated.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical investigation of reduction of mercury complexes of 2-aminocyclopentene-1-dithiocarboxylic acid and some of its derivatives at mercury electrodes

Safavi¹,

Gholivand²

1996

Electrochemical techniques of polarography, cyclic voltammetry, and controlled potential electrolysis at mercury electrodes have permitted a detailed investigation of the reduction reactions associated with mercury 2-aminocyclopentene dithiocarboxylate complexes, Hg(ACD),, in dimethyl sulphoxide (DMSO). As a complementary study, the electrochemistry of the ligands themselves was investigated in DMSO solutions and at mercury electrodes. The lability of mercury(I1) complexes and their rapid interaction with elemental mercury strongly influence the nature of the redox processes observed at mercury electrodes. Reduction of Hg(ACD), at a mercury electrode occurs in an overall two-electron step as: although mercury (1)

“…Oxidation of dithiocarbamato complexes of mercury with halogen results in the oxidation of the ligand yielding thiuram disulfide coinplexes (1). However, the reactions of mercury(I1) halides with tetraethylthiuram disulfide (TETD) often yield dithiocarbamato complexes (2, 3).…”

Section: Introductionmentioning

confidence: 99%

Crystal structure of mercury(II) bromide dithiocarbamate, [HgBr₂(S₂CNEt₂)Hg(S₂CNEt₂)]_n, an inorganic polymer

Chieh¹

1978

A pale yellow crystal obtained from reaction of HgBr2 and tetraethylthiuram disulfide (TETD) has the composition of HgBr2•Hg[S2CN(C2H5)2]2. TETD was reduced to dithiocarbamate. The molecules are polymeric chains with HgBr2 and Hg2+ alternately bridging to dithiocarbamate ions and vice versa. The crystal is monoclinic: a = 10.421(7), b = 15.244(13), c = 14.649(8) Å, β = 113.3(1)°; space group P21/c. The final R factor for 2085 observed reflections is 0.083. There are two types of coordination geometries for the mercury(II) ions in the crystal: the coordination for one is digonal with two short Hg—S distances of 2.385(11) and 2.365(10) Å. The coordination for the other is tetrahedral with two Hg—S, 2.552(10) and 2.569(10) Å, and two Hg—Br, 2.640(4) and 2.552(7) Å, bonds. The average C=S distance is 1.72(4) Å.