Dithiocarbamates cation

An aged carbonylated ruthenium chloride solution reacts with tetrabenzyl-dithiaramyl disulfide to produce a dithiocarbamate cation (170). 

Figure 176. Schematic representations of octahedral mixed-diamine-dithiocarbamate cations.

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... 

These short Au-Au contacts may be compared with distances of 2.88 A in metallic gold and 2.60 A in gaseous Au2. The term aurophilicity has been coined by H. Schmidbaur to describe the phenomenon [189,194], The interactions can occur as pairs, squares, linear chains or two-dimensional arrays of gold centres. Examples include the association between dimer units in the dithiocarbamates Au(dtc)2 (Figure 4.16) and the ionic tetrahydrothiophen complexes Au(tht)2 AuXJ (X = halogen), where cations and anions stack with Au—Au 2.97-2.98 A (X = I). The interaction is such that Au(S203)2 pair up, despite their charge, with Au-Au 3.24 A in the sodium salt. Likewise in Aupy AuCl, cations pair up at 3.42 A apart [10, 195]. 

The direct reaction of [TCO4] in ethanolic solution with dppe and oxalic acid produces the red Tc" complex [Tc(ox)(dppe)2] (552). Attempts to prepare similar complexes with succinic acid, phthalic acid, or salicylic acid failed, or the complexes were stable in solution only. " Similarly, cationic complexes of Tc" are produced by reaction of the versatile precursor [TcO(OH)(dppe)2] (204) with various dithiocarbamates, which produces several complexes of general formula [Tc(dtc)(dppe)2] (553). For this reaction the reductant formamidine sulphinic acid (510) was required in an alkaline solution. The X-ray crystal structure of [Tc(S2CNMe2)(dppe)2] (554) shows a distorted octahedral geometry. Cyclic voltammetry reveals a reversible reduction wave Tc"/Tc couple at —0.53 V, and a reversible oxidation at +0.3 V for the Tc" /Tc" couple. The same compound (554) was also prepared from the thiourea precursor [TcO(tmtu)4] + (91).The reaction of this precursor in dmf in the presence of dppe produced a mixture of brown [TcO(dtc)(tmtu)2] and the Tc" complex (553). The first compound is probably an intermediate... 

Coordinated transition metal redox-active macrocycles, 39 108-124 ammonium cation, 39 128-133 crown ether and bis crown ether ligands containing bipyridyl transition metal recognition sites, 39 111 crown ether dithiocarbamate and dithiolene complexes, 39 123-124 metalloporphyrin crown ether compounds, 39 108-109... 

Upon oxidation, certain dithiocarbamate complexes yield the 3,5-bis(jV,iV-dialkyliminium) trithiolane-1,2,4 cation (628). The structure of the [Hg216 ]2 salt of this cation (R = Et) has been determined (29) (Fig. 5). 

The formation of chloroimino ligands has been proposed solely on weak v(C=N) vibrations in the 1600-1750 cm-1 IR region. A repeat of the vanadium reaction by other workers (109) found the product of their reaction to be VC13(CNBu )3, so some caution should be applied to the formulation of the proposed vanadium dimer at least. Substitution reactions on these compounds with a series of mono- and bidentate tertiary phosphorus ligands and metathetical replacements with lithium quinolin-8-olate and sodium diethyl dithiocarbamate have given a range of neutral and cationic products (204, 483). 

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