Metal derivatives of heterocyclic-2-thiones: Variable donor ability, C-S rupture and new structural motifs

Journal of Chemical Sciences

Tarlok S Lobana1¹  Razia Sultana¹ 

[1] Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India$$

关键词: Heterocyclic-2-thiones;    pyridine-2-thione;    copper;    silver;    polynuclear;    C-S rupture.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

The chemistry of thio-ligands based on heterocyclic-2-thiones, namely, pyridine-2-thione (SNC5H5), imidazolidine-2-thione (SN2C3H6), imidazoline-2-thione (SN2C3H4), 1-methyl-imidazoline-2-thione (SN2C4H6) and thiazolidine-2-thione (S2NC3H5) with coinage and some other metals are described. The synthesis, solvent effect, isolation of new products after C-S rupture and crystal structure are also discussed. For example, copper(I) bromide with 1-methyl-imidazoline-2-thione (SN2C4H6) in acetonitrile formed CuI trinuclear complex, {Cu3(𝜅1-Br)3(𝜇-SN2C4H6)3}·CH3CN. This reaction in the presence of chloroform involved C-S bond rupture, oxidation of sulphur to sulphate and bromination of ring and formed a tetranuclear cluster, Cu4(𝜅1-N-(N2C4H5Br)4(𝜇4-O)(𝜇-Br)6] (N2C4H5Br = 2-bromo-1-methyl-imidazole). The reaction of copper(I) chloride with 1-methyl-imidazoline-2-thione (SN2C4H6) in acetonitrile also involved C-S rup ture and formed a chloro-bridged dinuclear complex [Cu2{𝜅2-N,N-(N2C4H5)2S}2(𝜇-Cl)2Cl2] {(N2C4H5)2S = 1, 1'-dimethyl-2,2'-di-imidazolyl sulphide}. Significantly copper(I) bonded to more polarisable iodide ion (Cu-I) does not involve C-S rupture and in this case it formed CuI polynuclear complex, {Cu2(𝜇-I)2(𝜇-SN2C4H6)2}𝑛. Both copper(I) chloride and copper(I) bromide with 1-methyl-imidazoline-2-thione in dimethyl sulphoxide involved C-S rupture and oxidation of sulphur to sulphate and formed a sulphate chelated CuII complex, [CuII{𝜅2-N,N-(N2C4H5)2S}(𝜂2-O,OSO2)(𝜅1-OH2)]. Imidazolidine-2-thione (SN2C3H6) with copper(I) chloride/bromide in dimethyl sulphoxide gave a sulphate bridged polynuclear complex, [CuII{𝜅2-N,N-(N2C3H5)2S}(𝜇-O,OSO2)(𝜅1-OH2)]𝑛 {(N2C3H5)2S = 2,2'-thio-di-2-imidazoline}. Other metals such as silver, zinc, cadmium and mercury formed monomers or dimers.

【 授权许可】

Unknown