Syntheses And Structures Of Polynuclear Silver(I) Clusters With Thiolate Ligands

Syntheses,structures and properties of a serial polynuclear silver（I） clusters with thiolate ligands were reported in this paper.Various silver（I） salts were selected to react with mercaptan andα-C₁₀H₇CS₂^-respectively,a series of silver（I） -sulfur clusters with novel structures were isolated and characterized.Reaction of[(α-C₁₀H₇CS₂)Ag]with dppb[1,4-bis（diphenylphosphino）butane]in a ratio of 1:1 in dichloromethane led to a one-dimensional chain polymer namely[Ag(α-C₁₀H₇CS₂)dppb]_n（1）.Treatment of[(α-C₁₀H₇CS₂)Ag]with pyridine afforded the isolation of[Ag₄(α-C₁₀H₇CS₂)₄（py）₄]·py（2）which was a deformed quadrilateral Ag₄ core that coordinated by pyridine.An ionic cluster with planar quadrilateral Ag₄ core,[Et₄N]₂[Ag₄(α-C₁₀H₇CS₂)₆]（3）,was obtained through the interaction of silver halides with two equiv.[（Et₄N）(α-C₁₀H₇CS₂)]in hot DMF solution.Depolymerization of silver thiolate[（RSAg）_n,R=ⁱPr,ⁱBu,^tBu]by TfaAg（silver trifluoroacetate）in methanol,the reaction of Tfa Ag with（ⁱPrSAg）_n in a ratio of 2:1 in the presence of dppe[1,2-Bis（diphenylphosphino）ethane]gave a three-dimensional polymeric cluster[Ag₄（μ₃-S）₄（dppe）₂]_n（4）with the scission of the S-C bond of ⁱPrS^-from the hot methanol solution.Similar reaction of TfaAg with（ⁱPrSAg）_n at room temperature easily gave rise to a one-diamensional chain cluster namely{[Ag₁₂（μ₂-O）（μ₂-tfa）₅（η¹-tfa）（μ₄-SⁱPr）₆（OMe）₃（H₂O）₂]·2H₂O}_n（5）,which was formed by bridging Ag₁₂S₆ cage through Tfa^-and O^2-.With silver（I） iodide suspended in carbon disulfide and chloroform,a two-dimensional network cluster[Ag₁₈（μ₄-I）₆（μ₃-I）₄（μ₂-I）₂（μ₃-SⁱPr）₈]_n（6）was isolated from the reaction of silver（I） iodide with isopropyl mercaptan.While（ⁱPrSAg）_n was selected to react with potassium iodide,with silver atoms bridged byμ₃-S atoms,a one-dimensional nanotube structure[Ag₃₆（μ₈-I）₄（μ₇-I）₂（μ₃-SⁱPr）₃₀]_n（7）was formed,in which the iodide was centrally distributed.Structures of all clusters was confirmed by single-crystal X-ray diffraction and the characteristics of electron transition was analyzed by solid-state UV/vis absorption spectra.