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(硫代酰胺)-I2 加合物对金的氧化溶解。

Gold oxidative dissolution by (thioamide)-I2 adducts.

机构信息

Dipartimento di Scienze Chimiche e Geologiche Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, I-09042 Cagliari, Italy.

出版信息

Dalton Trans. 2013 Jan 14;42(2):492-8. doi: 10.1039/c2dt31855e. Epub 2012 Oct 19.

Abstract

Elemental gold powder is easily oxidised under mild reaction conditions with 1 : 1 I(2)-adducts of the thioamides 3-methyl-benzothiazole-2-thione (mbtt) and 1-methyl-1H-benzimidazole-2(3H)-thione (mbit) with separation of the ionic complexes [Au(I)(mbtt)(2)]I(3) (1) and (mtbiH)(2)I(3) (2) [mtbiH = the imido protonated form of 2-(methylthio)benzimidazole] (gold oxidation yield >78% and 45%, respectively). The X-ray crystal structure of 1 shows the Au(i) centre linearly bound by two neutral ligands via the sulphur atom, whereas the X-ray crystal structure of 2 shows the Au(III) centre surrounded by four iodides in a square-planar arrangement. The oxidising/complexing properties of the mbtt·I(2) and mbit·I(2) adducts were interpreted considering the S-donor to I(2) interaction that leads to a charge separation between the I(b) and I(t) iodine atoms in the fragment S-I(b)-I(t). The oxidation of gold in a non-aqueous solvent by thioamide-I(2) adducts could be a promising alternative process to the numerous hydrometallurgical ones for the recovery of gold from secondary sources.

摘要

元素金粉在温和的反应条件下很容易被氧化,与硫代酰胺 3-甲基苯并噻唑-2-硫酮 (mbtt) 和 1-甲基-1H-苯并咪唑-2(3H)-硫酮 (mbit) 的 1:1 I(2)-加合物反应,生成分离的离子配合物 [Au(I)(mbtt)(2)]I(3) (1) 和 (mtbiH)(2)I(3) (2) [mtbiH = 2-(甲硫基)苯并咪唑的亚氨基质子化形式](金的氧化产率分别为>78%和 45%)。1 的 X 射线晶体结构表明 Au(i) 中心通过硫原子线性结合两个中性配体,而 2 的 X 射线晶体结构表明 Au(III) 中心被四个碘原子在正方形平面排列中包围。mbtt·I(2) 和 mbit·I(2) 加合物的氧化/络合性质通过 S 供体与 I(2) 的相互作用来解释,这导致 S-I(b)-I(t) 片段中 I(b)和 I(t)碘原子之间的电荷分离。在非水溶剂中通过硫代酰胺-I(2) 加合物氧化金可能是从二次资源中回收金的众多水冶金工艺的有前途的替代工艺。

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