Synthesis and infrared spectra of some dithiocacodylate complexes

Abstract

The synthesis of dithiocacodylate complexes of the metals chromium(111), indium(111), manganese(11), cobalt(11), nicke1(11),� zinc(11), and copper(1) is described. The compounds can be prepared either from sodium dithiocacodylate Na[S2As(CH3)2] or by passing hydrogen sulphide through a methanolic solution of the metal cacodylate in the presence of hydrogen chloride. The infrared spectra in the region 4000-40 cm-1 of the new compounds have been recorded and assigned by a comparison with the spectra of several compounds which are closely related. The arsenic-sulphur and metal-sulphur stretching frequencies occur in the region of 450 cm-1 and 260-340 cm-1, respectively.

The Lewis-base behavior of Bunsen's cacodyl disulfide, Me2As(S)‒S‒AsMe2, toward molecular halides of group 13

“…Bunsen found that the reaction of 2 with CuCl 2 and AuCl 3 gave the complexes Me 2 AsS 2 M [M¼Cu(I), Au(I)] and we and others confirmed the production of Cu(I) complex starting from 2 and from 7 [5,6].…”

“…Although InCl 3 reacts with Me 2 AsS 2 Na Á 2H 2 O 7 to give (Me 2 AsS 2 ) 3 In, [6,7] InCl 3 simply binds to 2, Figure 2(i)-(vi). From the downfield shifting of the singlets, the dominant binding is on the As¼S sulfur.…”

“…Many complexes (Me 2 AsS 2 ) x M have been prepared, generally by reacting 2 with heavy metal cations [1,5,6] or using the salt Me 2 AsS 2 Na Á 2H 2 O 7 [6,20]. Bunsen found that the reaction of 2 with CuCl 2 and AuCl 3 gave the complexes Me 2 AsS 2 M [M¼Cu(I), Au(I)] and we and others confirmed the production of Cu(I) complex starting from 2 and from 7 [5,6].…”

“…We wondered if In(III) in InCl 3 is able to give L 3 In from 2. L 3 In has been previously prepared from Me 2 AsS 2 Na Á 2H 2 O 7 and studied crystallographically [6,7]. To complete the study with the Lewis acids of group 13, we studied the reaction of 2 with thallium(III) acetate.…”

“…We studied this nucleophilic activity of 2 with several heavy metal cations paying attention to the required conditions for obtaining pure complexes L x M, [5] because impure ones can sometimes be formed [6]. We found that the L x M complexes are not stable in the presence of their own M xþ ions, giving colored insoluble solids, and the arsenium ion Me 2 As: þ reacts preferably with 2, Equation (5), in the presence of other nucleophiles, e.g.…”