Synthesis of 1,1′-Bis(1-Methyl/Chloro-2,3,4,5-Tetraphenyl-1-Silacyclopentadienyl) [Ph(4)C(4)Si(Me/Cl)-(Me/Cl)SiC(4)Ph(4)] from Silole Anion [MeSiC(4)Ph(4)](−)•[Li(+) or Na(+)] and Silole Dianion [SiC(4)Ph(4)](2−)•2[Li(+)]; Oxidative Coupling of Silole Anion [MeSiC(4)Ph(4)](−)•[Li(+) or Na(+)] by Ferrous Chloride (FeCl(2)) and Oxidative Coupling and Chlorination of Silole Dianion [SiC(4)Ph(4)](2−)•2[Li(+)] by Cupric Chloride (CuCl(2))

A reaction of silole anion {[MeSiC(4)Ph(4)](−)•[Li(+) or Na(+)] (1) with anhydrous ferrous chloride (FeCl(2)) in THF (tetrahydrofuran) gives 1,1′-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph(4)C(4)Si(Me)-(Me)SiC(4)Ph(4)] (2) with precipitation of iron metal in high yield. Silole dianion {[SiC(4)Ph(4)](2−)•2[Li(+)] (3) is added to anhydrous cupric chloride (CuCl(2)) in THF at −78 °C, then the dark red solution changes into a greenish solution. From the solution, a green solid is isolated, and stirring it in toluene at room temperature provides quantitatively 1,1′-bis(1-chloro-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph(4)C(4)Si(Cl)-(Cl)SiC(4)Ph(4)] (4) with precipitation of copper metal in toluene. The green solid is suggested to be 1,1′-bissilolyl bisradical [Ph(4)C(4)Si-SiC(4)Ph(4)](2•) (8), and lithium cuprous chloride salts {[Li(2)Cu(I)Cl(2)](+)•[Cu(I)Cl(2)](−)}. Both reactions are initiated by single-electron transfer (SET) from the electron-rich anionic silole substrates (1 and 3) to iron(II) and copper(II).