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

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• 作者：Tatyana A. Rodina^a ; Alexander V. Ivanov^a ; ^{alexander.v.ivanov@chemist.com} ; Andrey V. Gerasimenko^b ; Olga V. Loseva^a ; Oleg N. Antzutkin^c ; ^d ; Valentin I. Sergienko^b
• 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 (ng class="boldFont">1ng>); X = [Cd₂Cl₆]2鈭?/sup>, R = C₃H₇ (ng class="boldFont">2ng>)) and [Au(S₂CNR₂)₂][AuCl₄] (R = iso-C₃H₇ (ng class="boldFont">3ng>); R = iso-C₄H₉ (ng class="boldFont">4ng>)) 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 (ng class="boldFont">1ng>-ng class="boldFont">4ng>), 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 ng class="boldFont">3ng> and ng class="boldFont">4ng>) has four neighbouring chlorine atoms [AuCl₄]. At the supramolecular level, compounds ng class="boldFont">1ng> and ng class="boldFont">2ng> 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 ng class="boldFont">3ng> and ng class="boldFont">4ng>. 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 ng class="boldFont">3ng> and ng class="boldFont">4ng>, respectively.}