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) 4 S 6 ] (A) revealed that the cluster core will be partly disassembled and a {PhSi} moiety is replaced by a coinage metal phosphine complex to form [(Et 3 PAg) 3 (PhSi) 3 S 6 ] (B) and [Na 2 (thf) 2.33 ][(Me 3 PCu)(PhSi) 3 S 6 ] (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(PMe 2 Ph) 3 ] (1) and [AgCl(PMe 2 Ph) 2 ] 2 (2), the study addresses reactions of A with AgCl and a phosphine ligand in CH 2 Cl 2 , upon which A is completely disassembled to form [(Ph 3 P) 3 Ag(μ-S)SiCl 2 Ph] (3). In another case a CH 2 group, most likely stemming from CH 2 Cl 2 , was attached to the ligand, thus generating [{PhCl(S)SiSCH 2 P(Ph 2 )CH 2 CH 2 } 2 ] (4). Upon using CuCl and 1,4-bis(diphenylphosphino)butane (dppb) we isolated the phosphine-bridged analog of B, [{(dppbCu 2 )CuP(Ph 2 )(CH 2 CH 2 )(PhSi) 3 S 6 } 2 ] (5). In order to receive the yet elusive silver homolog of C, we used PMe 2 Ph as a bulkier ligand. This way we generated a 2D coordination polymer of the desired composition, [Na 2 (thf) 1.5 ][(Me 2 PhPAg)(PhSi) 3 S 6 ] (6). UV-visible spectra of 6 indicated a bandgap of 3.89 eV, thus blue-shifted in regards to B and C.