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

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.