Copper dithiocarbamate complexes

They can react with metal-containing enzymes (e.g., polyphenoloxidase and ascorbic acid oxidase) to form a copper-dithiocarbamate complex with high fungicidal activity (thiram and ziram probably owe their fungicidal activity to this type of reaction). 

In other work, vibrational shifts for nickel and copper dithiocarbamate complexes have been correlated with those observed for atomic core levels in the X-ray photoelectron spectra (523), and an experimental procedure is detailed for the collection of high-quality IR spectra from metal dithiocarbamate singlecrystal surfaces using polarized radiation and attenuated total reflectance (524). 

Electrochemistry of copper dithiocarbamate complexes in a conventional electrochemical cell... 

Dithiocarbamate complexes of copper have been sythesized at a high rate. Reports of new complexes include the morpholine-4- (44), thio-morpholine, AT-methylpiperazine-4-, and piperidine- (291) dithiocarba-mates. Novel, polymeric complexes of the type Cu(pipdtc)2 (CuBr) in = 4, or 6) and Cu(pipdtc)2 (CuCl)4 have been prepared by reactions of[Cu(pipdtc)2] with the respective copper halide in CHCla-EtOH (418). The crystal structures of the polymers are known to consist of sheets of individual [Cu(pipdtc)2] molecules linked to polymeric CuBr chains via Cu-S bonds. A series of copper(I) dtc complexes have been the subject of a Cu and Cu NQR-spectral study (440). 

Copper Extraction of ammonium pyrrolidine dithiocarbamate complex with MIBK Miscellaneous < 0.5 pg/1 [374]... 

Yordanov, N. D., Shopov, D. EPR studies of dithiophosphate and dithiocarbamate complexes. Single-crystal study of bis(0,0 -diisopropyldithiophosphato)copper(ll). Chem. Phys. Letters 16, 60 (1972). 

In many complexes, mixed oxidation states for the transition metals are found. Complex (41) is a diamagnetic compound with the actual composition (42).68 Copper dithiocarbamates are synthesized not only with copper in the oxidation states I, II or III but also with the metal in mixed oxidation states III and I (43, 44, 45), II and I (46, 47) and even III and I [48, 49).56 Complex (50), which has two isomeric structures a and / , has Ru either in a trapped oxidation state II,in or in a delocalized oxidation state of 2.5. The /J-isomer is the most stable.69 Slow, controlled potential electrochemical oxidation of (51) yields (52), in which the metal has a trapped oxidation state II,HI.70... 

Although transesterification and transamidation reactions of simple carbonyl ligands are usually associated with the involvement of a co-ordinated nucleophile, there are some well-documented processes which unambiguously involve attack by an external nucleophile upon a co-ordinated electrophile. Dithiocarbamate complexes contain a chelated. S, 5"-bonded dithioamide ligand and undergo facile transamination reactions upon treatment of the copper complexes with amines (Fig. 3-22). 

Work by Paul Beer et al. in Oxford on dithiocarbamate-functionalised resorcarenes has resulted in resorcarene trimers termed molecular loops and molecular tetrahedra composed of four resorcarene units. The molecular loops (pyridine-capped Cd(II) and Zn(II) complexes) can bind C60 which fits neatly into the 16.4 A wide central cavity.35 The slightly larger tetrahedral tetramer which has a 19.4 A edge length, compared to 19.1 A for the loop, is bridged by square planar copper(III) ions, a very unusual oxidation state of copper that is obtained from iodine oxidation of an intermediate copper(II) complex. The solid-state structures of examples of the loop and tetrahedron are shown in Figure 10.35. 

Analogous steric effects of bulky substituents at the nitrogen atom have been also reported for copper(II) dithiocarbamate complexes [71]. 

Manganese, zinc and iron dithiocarbamates, whether they are 1 1 or 2 1 complexes, react with copper-containing complex compounds, thus with proteins,... 

Alkylindium thiolate complexes readily react with copper dithiocarbamate compounds to yield binuclear complexes, according to Scheme No structural data is available for these mixed metal complexes however, they have been... 

Viola-Rhenals, M., Strasberg Richer, M., Rieber, M. (2006) Suppression of survival in human SKBR3 breast carcinoma in response to metal-chelator complexes is preferential for copper-dithiocarbamate. Biochemical Pharmacology, 71,722-734. 

Very often it is possible that oxidation-reduction reactions occur between the copper chelate complex and the base as a result the chelate ligands are removed from the first coordination sphere and new complexes showing catalytic activity are obtained. Similar oxidation-reduction reactions were established in the reaction of acetylacetonate, oxine, thioxine, dithiocarbamate, dithiophosphate, etc., complexes with strong Lewis bases, such as triphenylphosphine (10), piperidine, pirrolidine(ll), ammonia(6,12) etc. 

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