The Tricarbonyliron Chalcogenolates [(OC)(3)Fe(mu-ESitBu(3))](2) (E = S, Se, Te)

The tricarbonyhron thiolate and selenolate [(OC)(3)Fe(mu-ESitBu(3))](2) (E = S, Se) were synthesized photochemically from the reaction of 2 equiv. of pentacarbonyliron with the dichalcogenides tBu(3)Si-E-2-SitBu(3) (E = S, Se). X-ray-quality crystals of the tricarbonyhron thiolate [(OC)(3)Fe(mu-SSitBu(3))](2) (monoclinic, P2(1)/n) and selenolate [(OC)(3)Fe(mu-SeSitBu(3))](2) (monoclinic, P2(1)/n) were grown from benzene. The cyclic voltammograms of [(OC)(3)Fe(mu-ESitBu(3))](2) (E = S, Se, Te) resemble each other. Electrochemical reduction at potential below -2.2 V or reduction of [(OC)(3)Fe(mu-ESitBu(3))](2) (E = S, Se, Te) with Na or K led to degradation of the complex core with the formation of the chalcogenolates [ESitBu(3)]. (E = S, Se, Te). The dichalcogenides tBu(3)Si-E-2-SitBu(3) (E = Se, Te) are accessible by the reaction of Na[ESitBu(3)] with oxygen. However, the disulfide tBu(3)Si-S-2-SitBu(3) (monoclinic, P2(1)/c) which is used in the synthesis of tricarbonyliron thiolates [(OC)(3)Fe(mu-ESitBu(3))](2) as starting material, was prepared from S2Cl2. and Na[SitBu(3)]. Depending on the solvent used for crystallization, the sodium supersilyl chalcogenolates Na[ESitBu(3)] (E = S, Se) form dimeric or tetrameric structures in the solid state. Single crystals of the dimeric thiolate [Na(thf)(2)SSitBu(3)](2) (monochnic, P2(1)/c) were obtained from thf at -25 degrees C whereas crystals suitable for X-ray diffraction of tetrameric chalcogenolates [Na(thf)ESitBu(3)](4) (E = S, Se) were grown from hexane at -25 degrees C.