Gold(III) ionic complexes [Au{S2CN(C2H5)2}2]Cl and ([Au{S2CN(C2H5)2}2][AuCl4]) n : Synthesis, supramolecular self-assembly, polymorphism, and thermal behavior

Abstract

A heterogeneous reaction between freshly precipitated oxovanadium(IV) diethyldithiocarbamate [VO{S 2 CN(C 2 H 5 ) 2 } 2 ] and a solution of AuCl 3 in 2 M HCl has been shown to yield two ionic gold(III) com pounds: the water soluble ionic complex [Au{S 2 CN(C 2 H 5 ) 2 } 2 ]Cl (I) and the coordination polymer ([Au{S 2 CN(C 2 H 5 ) 2 } 2 ][AuCl 4 ]) n (II), which was preparatively separated from the precipitate phase. The molecular and crystal structures of the synthesized complexes have been established by X ray diffraction. The crucial role in the supramolecular self assembly of the compounds obtained belongs to C-H⋅⋅⋅Cl hydrogen bonds (in I) and Au⋅⋅⋅S and Au⋅⋅⋅Cl secondary interactions (in II). Polymeric complex II has been found to be able to form two polymorphs, which differ from each other by the building mode of cation-anion poly meric chains. The study of the thermal behavior of the synthesized complexes by simultaneous thermal anal ysis in an argon atmosphere has allowed us to recognize conditions for the recovery of bound gold. In both cases, reduced metallic gold is the only final thermolysis product.

Uncommon and Emissive {[Au2(C3H6NS2)2][Au(C3H6NS2)2]2(PF6)2} Mixed Au+ and Au3+ Pseudotetranuclear Crystalline Compound: Synthesis, Structural Characterization, and Optical Properties

“…The Au–S covalent bonds have lengths ranging from 2.3365(13) to 2.3462(13) Å (Table ). Secondary bonds of the type Au···S were reported in the literature as being weaker than the Au–S covalent bonds, with secondary bonds reported in the literature usually ranging from 3.365(3) to 3.951(2) Å; , in the prepared complex herein presented, the value 3.4580(2) Å is in accordance with the already published values. Figure shows the unit cell content of the triclinic crystalline lattice.…”

“…It is an example of a mixed oxidation Au + and Au 3+ coordination compound. This kind of complex is not so common in the literature; to the best of our knowledge, few structures of this class of coordination compound have so far been characterized in X-ray studies. − The molecular structure is presented as a cationic complex stabilized by a two [PF 6 ] − anion. The subunit that contains two Au + atoms (Au 2 (C 3 H 6 NS 2 ) 2 ) is bonded concomitantly to two subunits [Au­(C 3 H 6 NS 2 ) 2 ] 2 that contain two Au 3+ atoms through μ 2 -S···Au secondary bonds (Au2–S2 and Au2#1–S2#1 of 3.4580(2) Å).…”

Expanding the Library of Dithiocarbamato-Carboxylate Metalloligands for Heterobimetallic Coordination Networks toward Copper and Gold

“…Less surprisingly, the +3 charge of the Au centers results in a fundamentally different solid-state structure than is seen with the related Cu, Pd, and Pt systems 8–10 , and consequently, Au­(III)-DTCC metalloligands deserve further investigation in combination with oxophilic metal ions other than Sr 2+ in future research. Generally, literature examples for structurally characterized CNs containing trivalent gold as nodes are exceptionally rare, , and the hitherto use of Au­(DTC) 2 + units as building blocks is limited to supramolecular assemblies with weak Au···Cl or Au···S linkages to the best of our knowledge. , …”

The Coordination Chemistry of Imidomethanedithiolate Di-anions: A Structural Comparison with Their Dithiocarbamate Analogs

“…The centrosymmetric square planar (S 4 ) molecular structures of 29-31 have much precedence in the literature, as exemplified by the salt [Au(S 2 CNEt 2 ) 2 ]Cl [63]. The Au-S bond lengths in the latter (i.e., 2 × 2.33 Å) lie in the range of 2.32-2.34 Å noted for the Au-S bonds in 29-31.…”