Dithiocarbamates of transition group elements in “unusual” oxidation states

A linear piperazine-pyridine ligand and its Hg coordination polymer

Publisher Summary Recently, an article was published on 1,2-dithio ligands, and have stressed the versatility of these ligands and the academic and industrial importance of their metal complexes. Complexes of molybdenum and tungsten with bidentate sulfur ligands have been investigated extensively. In recent years, the work in this field has been escalated by the impetus of designing models of such bioinorganic enzymes as nitrogenase and xanthine oxidase. Oxidation of copper dithiocarbamate complexes of Cu(1) with chlorine or bromine yields paramagnetic compounds with the composition CuX 3 (R 2 dtc), in which the copper has a formal oxidation-state of (IV), but the structure of these compounds is obscure. The complexes of the 1,1-dithio ligands with the Group I transition metals have been studied in considerable detail and have been extensively reviewed by Coucouvanis.

1, 1-Dithiolato Complexes of the Transition Elements

The complexes of rhodium (III), iridium(III), palladium(II) and platinum(II) with piperidine-, piperazine-, N-methylpiperazine-, morpholine- and thiomorpholine-dithiocarbamate have been prepared and characterized by spectroscopic methods. From the electronic absorption spectra the values of the ligand field parameters were determined. The nephelauxetic parameters are indicative of a strong covalency in the metal-ligand bond. A monomeric structure for the complexes is suggested. All the new compounds here reported are diamagnetic.

Dithiocarbamate Complexes of Rhodium(III), Iridium(III), Palladium(II) and Platinum(II)

The chemistry of the dithioacid and 1,1‐dithiolate complexes, 1968‐1977

Piperidine-, thiomorpholine-4- and n-methylpiperazine-4-carbodithioate transition metal complexes

Die bis-Acetato- und Propionato-Metalladdukte von Piperidin-(pipd), Piperazin(pipz), N-Methylpiperazin(CH3-pipz) und Morpholin(morph) wurden in festem Zustande isoliert und optisch und magnetisch untersucht. Piperazin bildet 1:1-Komplexe, die anderen Amine bilden 1:2-Komplexe. Die IR-Spektren ergeben, das die Amine an das Metallatom uber das N-Atom koordiniert sind, Acetat und Propionat sind symmetrische oder asymmetrische zweizahnige Liganden. In Monopiperazin-Addukten verbruckt das Amin zwei Metallatome. Elektronenspektren und magnetische Momente weisen auf eine transoktaedrische Konfiguration der Addukte.



Acetato- und Propionato-Komplexe gesattigter N-Heterozyclen mit CoII, NiII und CuII



The bis acetato and propionatometal-adducts of piperidine (pipd), piperazine (pipz), N-methylpiperazine (CH3-pipz) and morpholine (morph) are isolated in the solid state and investigated by spectral and magnetic measurements. Piperazine forms 1:1 complexes, the other amines 1:2 complexes. The infrared spectra show that the amines are coordinated to the metal atom toward the nitrogen atom and that the acetate and propionate act as symmetrical or asymmetrical bidentate ligands. The i.r. spectra give also evidence that in monopiperazine adducts the amine “bridges” two metal atoms. Electronic spectra and magnetic moments suggest a tran-octahedral configuration of the adducts.

G. C. Pellacani

Papers

Piperidine-, thiomorpholine-4- and n-methylpiperazine-4-carbodithioate transition metal complexes

Acetato‐ and Propionato‐(Saturated Heterocyclic) Amine Complexes of Cobalt(II), Nickel(II), and Copper(II)

Acetato- and propionato-(saturated heterocyclic) amine complexes of cobalt(ii), nickel(ii) and copper(ii)