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Issue 20, 2012
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Group 12 metal zwitterionic thiolate compounds: preparation and structural characterization

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Abstract

Reactions of TabHPF6 (Tab = 4-(trimethylammonio)benzenethiolate) with three equiv. of M(OAc)2·2H2O (M = Zn, Cd) gave rise to two tetranuclear adamantane-like compounds, [M4(μ-Tab)6(Tab)4](PF6)8·S (1·S: M = Zn, S = DMF·4H2O; 2·S: M = Cd, S = DMF·5H2O). The similar reactions of MCl2 (M = Zn, Cd, Hg) with four equiv. of TabHPF6 in the presence of Et3N afforded three mononuclear compounds [M(Tab)4](PF6)2·S (3·S: M = Zn, S = 2(H2O)0.5; 4·S: M = Cd, S = 2(H2O)0.5; 5·S: M = Hg, S = 2DMF). Treatment of the precursor complex 3 or 5 with equimolar MCl2 and two equiv. of TabHPF6 and Et3N produced one dinuclear compounds [M(μ-Tab)(Tab)2]2(PF6)4·2DMF·2H2O (6·2DMF·2H2O: M = Zn; 8·2DMF·2H2O: M = Hg) while analogous reactions of 4 with CdCl2·2H2O gave rise to [Cd(μ-Tab)2(Tab)]2(PF6)4·2DMF (7·2DMF). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR and single-crystal X-ray crystallography. In 1 or 2, four M2+ ions and six S atoms of Tab ligands constitute an adamantane-like [M4(μ-S)6] cage in which each M2+ ion is tetrahedrally coordinated by one terminal S and three bridged S atoms from four different Tab ligands. In 3–5, each M2+ center of the [M(Tab)4]2+ dication is tetrahedrally coordinated by four S atoms of Tab ligand. Two [M(Tab)2]2+ dications in 6 or 8 are further bridged by a pair of Tab ligands to form a dimeric [M(μ-Tab)(Tab)2]24+ structure. Each dimeric [(Tab)Cd(μ-Tab)2Cd(Tab)]4+ unit in 7 is linked to its two neighboring units via two couples of bridging Tab ligands, thereby generating a unique 1D cationic chain. These results may provide useful information on interpreting structural data of MTs containing group 12 metals.

Graphical abstract: Group 12 metal zwitterionic thiolate compounds: preparation and structural characterization

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Publication details

The article was received on 12 Feb 2012, accepted on 09 Mar 2012 and first published on 09 Mar 2012


Article type: Paper
DOI: 10.1039/C2DT30313B
Citation: Dalton Trans., 2012,41, 6162-6172
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    Group 12 metal zwitterionic thiolate compounds: preparation and structural characterization

    X. Tang, R. Yuan, J. Chen, W. Zhao, A. Zheng, M. Yu, H. Li, Z. Ren and J. Lang, Dalton Trans., 2012, 41, 6162
    DOI: 10.1039/C2DT30313B

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