Dimers and 2D Networks of Adamantane-Related Ternary Organosilicon Coinage Metal Sulfide Clusters.

Adamantane-type organotin sulfide clusters were recently shown to react with coinage metal phosphine complexes under replacement of an organic substituent by a metal-phosphine unit. An extension of such studies involving the silicon-based congener [(PhSi)S] (A) revealed that the cluster core will be partly disassembled and a {PhSi} moiety is replaced by a coinage metal phosphine complex to form [(EtPAg)(PhSi)S] (B) and [Na(thf)][(MePCu)(PhSi)S] (C). Herein, we present an extension of this work upon variation of the reactants and reaction conditions. Besides the isolation of crystalline precursor complexes [CuCl(PMePh)] (1) and [AgCl(PMePh)] (2), the study addresses reactions of A with AgCl and a phosphine ligand in CHCl, upon which A is completely disassembled to form [(PhP)Ag(μ-S)SiClPh] (3). In another case a CH group, most likely stemming from CHCl, was attached to the ligand, thus generating [{PhCl(S)SiSCHP(Ph)CHCH}] (4). Upon using CuCl and 1,4-bis(diphenylphosphino)butane (dppb) we isolated the phosphine-bridged analog of B, [{(dppbCu)CuP(Ph)(CHCH)(PhSi)S}] (5). In order to receive the yet elusive silver homolog of C, we used PMePh as a bulkier ligand. This way we generated a 2D coordination polymer of the desired composition, [Na(thf)][(MePhPAg)(PhSi)S] (6). UV-visible spectra of 6 indicated a bandgap of 3.89 eV, thus blue-shifted in regards to B and C.