Reactions of Sodium N,N-Diethyldithiocarbamate and Potassium Ethyl Xanthate with some 3d Transition Metal Halides in the presence of 2,2′-Bipyridyl and 1,10-Phenanthroline

Abstract

The synthesis and some properties of ethylxanthate (Xan-) complexes, MXanz and MXan,-(M = manganese(I1) and iron(11)) are reported. Reactions between divalent metal halides (manganese, iron, cobalt, nickel, copper, and zinc) and Xan-and between the metal halides and N,N-diethyldithiocarbamate (dtc-) in the presence of nitrogen bases 1,lO-phenanthroline (phen) and 2,2'-bipyridyl (bipy) are described. The major products of these reactions are complexes of the type MXan,.Base and Mdtcz.Base (with notable exceptions). I n the former series with bipy, two different crystalline modifications of the manganese, iron, and cobalt complexes are formed, and copper(I1) is reduced to copper(1) by Xan-in the presence of both bases. In the nickel-dtc system with bipy, Nidtc, is produced, while with phen, the complex [Niphen3]dtcz is formed. The latter reacts very rapidly with methylene chloride. Cudtc, is produced from the copper(II)/base/dtc reactions.

Spectroscopic, Thermal, Electrochemical, and Antimicrobial Studies of Mononuclear Manganese(II) Ditolyldithiophosphates

“…IR spectral assignments of these complexes ( 1 – 20 ) were made on the basis of relevant literature reports [26–28, 31, 32]. The comparison of IR spectra of these complexes with starting materials has also shown significant and characteristic changes and also shifting of bands.…”

“…The versatility of applications of dithiophosphates and their ability to combine with metal ions into a variety of coordination complexes have led to a large interest in their structure and the factors governing the properties of dithiophosphate complexes. The best known complexes of manganese with sulfur ligands are dithiophosphinates [26, 27] and the dithiocarbamates [28]. A perusal of the literature reveals no report on the manganese(II) ditolyldithiophosphates.…”

Crystal Structure of Bis(<i>O</i>-<i>n</i>-butyldithiocarbonato-<i>S</i>,<i>S</i>')(1,10-phenanthroline)-manganese(II)

“…The early syntheses of manganese(II) ethyl xanthates were accomplished in a nitrogen-filled glovebox. 2 Bivalent metal dithiocarbonates are known to form stable adducts with nitrogen donors which exhibit a variety of coordination geometries. 3 Coordination complexes of dithiocarbanto ligands with a variety of transition as well as non-transition metals have been reported, 4,5 owing to their wide applications in various fields, like metallurgy, rubber technology and medicines.…”

“…The crystal structure was solved by direct methods, and refined by full-matrix least-squares procedures to a final R-value of 0.0464 for 1892 observed reflections. In the title molecular complex, the butyl chain is disordered over two sets of sites, with occupancy ratios of 0.54(2): 0.46 (2). The crystal structure is stabilized with the help of p-p interactions between neighbouring pyridine rings, with a centroid-to-centroid distance of 3.849 Å.…”

“…The Mn-S bond lengths, Mn1-S1 = 2.6018(9)Å; Mn1-S2 = 2.5909(9)Å, are in good agreement with those reported for other Manganese dithiocarbonato complexes. 10 The butyl chain is disordered over two sets of sites, with occupancy ratios of 0.54(2):0.46 (2). Molecules in the unit cell comprise layers, which are anti-parallel to each other, whereas the molecules within the layers are parallel to each other.…”