Mercury(II) 2-Aminoethanethiolate Clusters: Intramolecular Transformations and Mechanisms
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- 作者：Mohan S. Bharara ; Sean Parkin ; David A. Atwood
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：September 4, 2006
- 年：2006
- 卷：45
- 期：18
- 页码：7261 - 7268
- 全文大小：168K
- 年卷期：v.45,no.18(September 4, 2006)
- ISSN：1520-510X
文摘
The combination of HgF2 and 2-aminoethanethiol (AET, with some AET·HCl present) yielded a cyclic tetranuclearthiolate, [Hg4Cl4(SCH2CH2NH2)4] (1), with alternating Hg and S atoms. The Cl from the reaction mixture led to theformation of Hg-Cl bonds with no Hg-F in the final product. In contrast, a similar reaction with HgBr2 yielded anonanuclear cluster, [Hg9Br15(SCH2CH2NH3)15]3+ (2), and the disulfide salt {[HgBr4][(NH3CH2CH2S-)2]} (3). Despitesimilar reactions, the AET groups in 2 are protonated compared to the nonprotonated amine groups in 1, whichallows the ligand to chelate the Hg atom in the latter compound. The reaction with HgI2 yielded a cyclic tetranuclearcompound, [Hg4I6(SCH2CH2NH2)2(SCH2CH2NH3)2](H2O/EtOH) (4), containing protonated and nonprotonated AETgroups. Compound 4 at room temperature irreversibly rearranges to [Hg4I4(SCH2CH2NH2)4] (5), which is isostructuralto 1. A systematic pathway for the formation of 1 along with the intramolecular conversion of 4 to 5 is proposed.These compounds demonstrate that very diverse Hg-S compounds form under similar reaction conditions.