Fixation modes of gold(III) from solutions using cadmium(II) dithiocarbamates. Preparation, supramolecular structure and thermal behaviour of polynuclear and heteropolynuclear gold(III) complexes: Bis(N,N-dialkyldithiocarbamato-S,S鈥?gold(III) polychloro
- 作者：Tatyana A. Rodinaa ; Alexander V. Ivanova ; alexander.v.ivanov@chemist.com ; Andrey V. Gerasimenkob ; Olga V. Losevaa ; Oleg N. Antzutkinc ; d ; Valentin I. Sergienkob
- 关键词：Polynuclear heteroleptic gold(III) complexes ; Heteropolynuclear gold(III)&ndash ; cadmium(II) complexes ; N ; N-Dialkyldithiocarbamate ligands ; Molecular and supramolecular structures ; 13C CP/MAS NMR spectroscopy ; Inorganic four-membered metallocycles ; Thermal
- 刊名：Polyhedron
- 出版年：2012
- 期刊代码：87_02775387
- 类别：ch
- 出版时间：19 June, 2012
- 卷：40
- 期：1
- 页码：53-64
- 文件大小：1137 K
摘要
Four novel heteropolynuclear and polynuclear complexes of the general formulae [Au(S2CNR2)2]2X (X = [CdCl4]2鈭?/sup>, R = CH3 (1); X = [Cd2Cl6]2鈭?/sup>, R = C3H7 (2)) and [Au(S2CNR2)2][AuCl4] (R = iso-C3H7 (3); R = iso-C4H9 (4)) were prepared using heterogeneous reactions between appropriate freshly precipitated binuclear cadmium(II) dialkyldithiocarbamates and AuCl3 in 2 M hydrochloric acid. The isolated complexes were studied by 13C CP/MAS NMR spectroscopy, single-crystal X-ray diffraction and simultaneous thermal analysis (STA) under an argon atmosphere. In all molecular structures (1-4), one of the gold atoms coordinates two dialkyldithiocarbamate ligands in the S,S鈥?bidentate mode, forming a square-planar coordination polygon [AuS4], while the other gold atom (in 3 and 4) has four neighbouring chlorine atoms [AuCl4]. At the supramolecular level, compounds 1 and 2 comprise binuclear cations, [Au2{S2CN(CH3)2}4]2+ and polynuclear chains, ([Au{S2CN(C3H7)2}2]+)n in a combination with [CdCl4]2鈭?/sup> and [Cd2Cl6]2鈭?/sup> anions, respectively. Unexpected structural distinctions at the supramolecular level were discovered for the chemically related compounds 3 and 4. In these ionic complexes, there are either cationic trinuclear formations, {[Au{S2CN(iso-C3H7)2}2]2[AuCl4]}+, or polynuclear chains, ([Au{S2CN(iso-C4H9)2}2]+)n, both combined with [AuCl4]鈭?/sup> anions, in the structural basis of compounds 3 and 4, respectively.