With dithiooxamide

The only recorded complex is the product of composition UF4 SC3N2H2 which results from the reaction of UF6 with dithiooxamide.137... 

Synthesis and IR and Raman spectra of deuterium labelled complexes of Ad" with dithiooxamides... 

Poly(3-alkylthiophene)s, having TT and electron-deficient thiazolo[5,4-J]thia-zole rings, were assembled through Stille cross-couplings (Scheme 27) [49]. Treatment of the aldehydes 122 with dithiooxamide (123) provided thiazolo[5,4-d] thiazole oligomers (124). Dibromination and then copolymerization with bis-stannane 126 produced air-stable polymers 127a-c. 

A few examples of early coordination polymerizations are noted here to provide a flavor for this work. The reaction of Cu(II) with dithiooxamides, reported by Kanda in 1962, gives a three-dimensional (3D) insoluble material (10) that has the catana-p, -(A(Ar -disubstituted dithiooxamido)copper stmcture." ... 

Aliphatic aldehydes and aryl methyl ketones did not furnish condensation products with dithiooxamide. F. 2,5-diarylthiazolo[5,4-d]thiazoles s. J. R. Johnson and R. Ketcham, Am. Soc. 82, 2719 (1960). 

In addition to stabilizing organic products by reaction with metal-exchanged clays, as indicated above, aluminosilicate minerals may enable the preparation of metal organic complexes that cannot be formed in solution. Thus a complex of Cu(II) with rubeanic acid (dithiooxamide) could be prepared by soaking Cu montmorillonite in an acetone solution of rubeanic acid (93). The intercalated complex was monomeric, aligned with Its molecular plane parallel to the interlamellar surfaces, and had a metal ligand ratio of 1 2 despite the tetradentate nature of the rubeanic acid. 

Diaminofurazan (DAF) (24) is a starting material for the synthesis of many nitro-substituted furazans and is readily prepared from the cyclization of 1,2-diaminoglyoxime (23) in the presence of aqueous base under pressure at 180 °C the latter prepared from the reaction of glyoxal/ glyoxime/ cyanogen or dithiooxamide with hydroxylamine. 

With hydrogen sulfide, the products are thiocyanoformamide, NCC(=S)NH2 and dithiooxamide, H2NC(=S)C(=S)NH2. 

With A,A-dimethyl- and N, TV-dicyclohexyl-dithiooxamide, Zn, Cd and Hg form the non-electrolyte MLX2 (X = Cl, Br or I) and electrolyte ML2X2 and ML3X2 (X = C104) complexes.8 9 IR studies show that all the complexes are S,N-coordinated for die ZnLX2 complexes, a tetrahedral coordination is indicated, while the analogous Cd complexes contain a halide-bridged octahedral structure. 

The reaction of dithiooxamide and its tetramethyl and tetraethyl derivatives with zinc, cadmium and mercury halides leads to complexes of stoichiometry MLX2 (M = Zn, Cd or Hg X = C1, Br or I).900,9 1 M—S bonding is involved IR spectra show that the zinc and mercury complexes are four-coordinate, while the cadmium complexes are octahedral with halogen bridges. 

Unless steric and electronic constraints prevail, vicinal dithiodiketones (10) can exist in an equilibrium mixture with their dithiacyclobutene (dithiete or dithietene) isomers (11). Strongly electron-withdrawing substituents, such as in (12), appear to favor the latter form, but the donor-substituted dithione (13) is also known22 to show such an equilibrium. As a czs-fixed dithiooxamide, the ligand (14) is particularly stable and presumably exists only in the dithione form. 

In contrast to the dithiolenes, we refer to dithiolato complexes as those in which the typical dithiolene resonance (and the properties which are associated with it) are absent because the ligand exists entirely in its dinegative form. In the neutral compound (22) above, the 2 — charge of the ethylenedithiolato ligand is balanced by the 2 + charge of the nickel atom and approximately square planar coordination is provided by the neutral dithiooxamide-type ligand. 

The thermal condensation of dithiooxamide with trichlorophenyl malo-nates results in thioamide 19, which with an excess of malonate gives a symmetric bis-TA 20. With other carbonyl compounds, thioamide 19 may be converted into other TAs with heterocyclic substituents, 21 and 22 (73JHC223) (Scheme 3). 

Similar insoluble salts form with many cationic chelates of heavy metal atoms. Thus, 12-molybdosilicic acid precipitates Cu+2, Ag+, Cd+2, Zn+2, Sn+2, Cr+3, Ni+2, and Co+2 in the presence of ethylenediamine, thiourea, hexamethylenetetramine, dithiooxamide, or similar chelating agents 106 ... 

The condensation product of dithiooxamide with benzaldehyde has been shown to be 2,5-diphenylthiazolo[5,4-d]thiazole (equation 75) (60JA2719). Its formation involves dehydration of the reactants and further dehydrogenation. The reaction is comparable in scope with condensations such as the Perkin reaction, and many 2,5-diarylthiazolo[5,4-c ]thiazoles have been prepared from a variety of aryl aldehydes. Condensation products were not obtained from simple aliphatic aldehydes (71JMC743). 

HFA inserts into an N—H bond of dithiooxamide with elimination of sulfur to yield monothiooxamide 139 (234). The X-ray structure of 139 shows the six atoms of the thiooxamide skeleton to be almost planar. 

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