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Issue 32, 2014
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Anion templating from a silver(I) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and decanuclear silver(I) clusters

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Abstract

We report on a Ag5 coordination polymer and discrete Ag8 and Ag10 dithiophosphate clusters. The cluster formation and structures were affected by the stoichiometric control of the M : L molar ratios used. The cluster [Ag5{S2P(OiPr)2}4]n(PF6)n, 1, is a monomeric unit within a coordination polymer formed through the reaction between [Ag(CH3CN)4]PF6 and the dithiophosphate ligand, [S2P(OiPr)2], used in a M : L molar ratio of 5 : 4. All other clusters formed in the study are discrete units with encapsulated anions within the metal framework. The clusters [Ag8(X){S2P(OiPr)2}6](PF6) (X = F, 2, Cl, 3, Br, 4) are all cationic and contain monoanionic halogens. The related cluster [Ag8(H/D){S2P(OiPr)2}6](PF6) contains either a hydride or a deuteride ion, 5 and 5′, respectively. The cluster [Ag8(S){S2P(OiPr)2}6], 6, is neutral due to the di-anionic nature of the encapsulated sulfide anion. Clusters 2–6 were all formed by reacting [Ag(CH3CN)4]PF6 and [S2P(OiPr)2] in a M : L molar ratio of 8 : 6 and stirring for 1 h in THF; thereafter the respective anions (one equiv.) were added in situ. The cluster [Ag10(I)4{S2P(OiPr)2}6], 7, is also neutral due to the charge balancing of the additional metal and halogen. In this case the M : L : X molar ratio was 10 : 6 : 4. All new clusters were characterized by 1H and 31P NMR, and elemental analysis, and 1, 2, 4–7 were characterized by single crystal X-ray diffraction.

Graphical abstract: Anion templating from a silver(i) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and decanuclear silver(i) clusters

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Publication details

The article was received on 07 Mar 2014, accepted on 16 Jun 2014 and first published on 03 Jul 2014


Article type: Paper
DOI: 10.1039/C4DT00691G
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 12380-12389
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    Anion templating from a silver(I) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and decanuclear silver(I) clusters

    J. Liao, H. Chang, Y. Li, C. Fang, B. Sarkar, W. E. van Zyl and C. W. Liu, Dalton Trans., 2014, 43, 12380
    DOI: 10.1039/C4DT00691G

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