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

We report on a Ag-5 coordination polymer and discrete Ag-8 and Ag-10 dithiophosphate clusters. The cluster formation and structures were affected by the stoichiometric control of the M: L molar ratios used. The cluster (Ag-5(S2P((OPr)-Pr-i)(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((OPr)-Pr-i)(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 [Ag-8(X){S2P((OPr)-Pr-i)(2)}(6)](PF6) (X = F, 2, Cl, 3, Br, 4) are all cationic and contain monoanionic halogens. The related cluster (Ag-8(H/D)(S2P((OPO2)-P-i}(6)](PF6) contains either a hydride or a deuteride ion, 5 and 5', respectively. The cluster [Ag-8(S)(S2P((OPr)-Pr-i)(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 [Ag-10(1)4{S2P((OPr)-Pr-i)(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 H-1 and P-31 NMR, and elemental analysis, and 1, 2, 4-7 were characterized by single crystal X-ray diffraction.