Alkali metal dithiocarbamato carboxylates (DTCCs) – synthesis, properties, and crystal structures

A series of alkali metal salts of dithiocarbamate‐substituted carboxylate (DTCC) anions were prepared by reaction of the parent amino acids with carbon disulfide and an alkali metal hydroxide. The target compounds, which were isolated in anhydrous form or as hydrates, were extensively characterized by elemental analyses, IR and NMR spectroscopy, thermal analyses, cyclic voltammetry, and single‐crystal X‐ray diffraction. The isolated compounds are more or less hygroscopic and display a varying dehydratization and decomposition behavior upon heating. The assumed degradation of the DTCC scaffold was found to depend on the substitution pattern as well as on the alkali metal counterion, and covers a range between 200 and 340 °C. In aqueous solution, the DTCC anions show irreversible electrochemical oxidations, where the corresponding redox potentials are governed by the substitution pattern of the nitrogen atom. Single‐crystal structural analyses of sodium and potassium derivatives revealed that these compounds exist as two‐ or three‐dimensional coordination polymers in the solid state, with the alkali‐metal ions adopting typical irregular coordination environments with coordination numbers of six or higher

Zn/Ni and Zn/Pd Heterobimetallic Coordination Polymers with [SSC-N(CH2COO)2]3− Ligands

In the construction of heterobimetallic coordination polymers based on dithiocarbamato–carboxylate (DTCC ligands), platinum as a thiophilic metal center can be replaced by the cheaper nickel or palladium. The compounds Zn[Pd(HL)2] and Zn2[M(L)2] (M = Ni, Pd; L = {SSC-N(CH2COO)2}3−) were prepared in a sequential approach starting from K3(L). The products were characterized by IR and NMR spectroscopy, thermal analyses, and single-crystal X-ray diffraction. The products decompose under nitrogen between 300 and 400 °C. Zn[Pd(HL)2] · 6H2O forms polymeric chains in the solid state, and the Zn2[M(L)2] · 14H2O (M = Ni, Pd) exhibit two-dimensional polymeric structures, each being isotypic with the respective Zn/Pt analogs. While the carboxylate groups in all these products are coordinated to zinc in a κO-monodentate mode, a structural variant of Zn2[Ni(L)2] having κO:κO′-briding carboxylate groups was also obtained. Exchange of the metal sites in the two Ni/Zn compounds was not observed, and these compounds are therefore diamagnetic

From Zero- to Three-Dimensional Heterobimetallic Coordination Polymers with the [Pt{SSC-N(CH2COO)2}2]4– Metalloligand

Heterobimetallic compounds of the type M’2[Pt(L)2] (L = N-dithioato-iminodiacetate, {SSC-N(CH2COO)2}3–) containing different bivalent, oxophilic metals M’ were prepared in a straightforward manner from [Pt(H2L)2] and the respective metal acetates, M’(OAc)2 (M’ = Mg–Ba, M–Cu, Cd). X-ray structure determination revealed that the products exist as zero- (Mg), one- (Mn), two- (Fe, Co, Ni, Cd), or three-dimensional (Sr) assemblies in the solid state. As a result, the water solubilities and thermal stabilities of the products cover much wider ranges than it has been seen with M’2[M(L)2] compounds having different thiophilic metal centers (M = Ni, Pd, Pt). While most of the compounds show a typical diamagnetic (Mg–Ba, Cd) or paramagnetic (Mn, Co, Ni, Cu) behaviour at ambient temperature, for Fe2[Pt(L)2] ·4 H2O an antiferromagnetic interaction of the Fe atoms is assumed. <br /