Cobalt complexes dithiocarbamates

The cobalt complex, Co(NO)[S2CN(CH3)2]2, is well characterized. - However, direct synthesis of itfrom the reaction between NO and Co[S2CN(CH3)2]2 leads to impure materials which are very difficult to purify. The ethylenedi-amine complex, Co(NO)(C2H4N2H4)2(Cl04)2, can readily be prepared in good yields and is easily converted into the dithiocarbamate derivative. The products from these reactions are obtained in a relatively pure form and can easily be further purified. 

Figure 177. Schematic representations of cobalt(III) dithiocarbamate etpb (L) complexes.

The alleged preparation of the supposed cobalt(II) complex Na[Co(Et2dtc)3] described by D Ascenzo and Wendlandt (305) has been repeated by Holah and Murphy (306), who identified the product as [Co(Et2dtc)3]. Complexes of cobalt(III), nickel(II), and palladium(II) salts with cationic, dithiocarbamate ligands have been synthesized (307). Reaction of the secondary amine (Et2N(CH2)2)2NH with CS2 produces... 

Cobalt(III) complexes of formula cis- and trans-[Co(dtc)L4]2+ and [Co(dtc)2L2]+ where dtc = dimethyl-, diethyl- or piperidino-dithiocarbamate were prepared with phosphites P(OMe)3, P(OEt)3 and 4-ethyl-2,6,7-trioxa-l-phophabicyclo[2.2.2]octane as ligands L.1048 Whereas Co—P bonding is found, as defined in the crystal structures of each of the two forms of complexes isolated, a linkage isomer in which the phosphite is O bound was detected for the bis(dithio-carbamate) compounds. 

Samples of metal complexes isolated from the final solutions were subjected to microanalysis (for carbon, hydrogen, oxygen, and sulfur). Metals were determined colorimetrically by the following methods— copper as the complex formed with sodium diethyl dithiocarbamate (6) cobalt as the nitroso-R salt complex (7) nickel as the dimethylglyoxime complex (4). 

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