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Complexes of the type ZnS6(TMEDA), ZnS4(PMDETA), and ZnS4(Me3TACN) react with electrophilic alkenes to give dithiolene complexes ZnS2C2R2(amine)n. The Me3TACN complex is the most reactive, while the more conveniently prepared PMDETA complex also undergoes this reaction at useful rates. The following alkenes were successfully tested: C2H2(CO2Me)2 (cis and trans isomers), C2H3(CO2Me), C2H3(CN), 1,2-C2H2Me(CN), C2H3(CHO), and 1,2-C2H2(CN)(Ph). Crystallographic analysis shows that the highly reactive complex ZnS4(Me3TACN) is structurally similar to ZnS4(PMDETA), including the presence of an elongated Zn−Nax bond. Model studies indicate that the reaction of alkenes with LnZnSx proceeds via the reversible formation of a dipolar intermediate, as indicated by the ability of the polysulfido complexes to catalyze the isomerization of cis-C2H2(CO2Me)2. It is proposed that such dipolar species undergoes ring closure to give alkanedithiolato intermediates, e.g., Zn[S2C2H2(CO2Me)2](PMDETA). The dithiolato complexes Zn...

Solutions of TiCl4 and ZnS6(TMEDA) react to give an amorphous, compositionally homogeneous binary titanium sulfide with the formula TiS∼9. In contrast to other binary metal sulfides, this material ...

The compounds (Ph4P)2[Ni2As4S8] (I), (Me4N)2[Mo2O2As2S7] (II), and (Et4N)2[Mo2O2As2Se7] (III) were synthesized by the hydrothermal reactions of NiCl2/K3AsS3/Ph4PBr, MoO3/K3AsS3/Me4NCl, and MoO3/K3A...

New chemical relationships have been established for C2-based carbon sulfides, as shown in the illustration below.

The [Pd7As10S22]4- molecule assembles under hydrothermal conditions from Pd2+ and [AsS3]3- to adopt the unusual shape of a gondola. Key to its formation appears to be the creation of direct Pd−As bonds.