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 {[MeSiC₄Ph₄]^&#8722;&#8226;[Li⁺ or Na⁺] (<b>1</b>) with anhydrous ferrous chloride (FeCl₂) in THF (tetrahydrofuran) gives 1,1&#8242;-bis(1-methyl-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph₄C₄Si(Me)-(Me)SiC₄Ph₄] (<b>2</b>) with precipitation of iron metal in high yield. Silole dianion {[SiC₄Ph₄]^2&#8722;&#8226;2[Li⁺] (<b>3</b>) is added to anhydrous cupric chloride (CuCl₂) in THF at &#8722;78 &#176;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&#8242;-bis(1-chloro-2,3,4,5-tetraphenyl-1-silacyclopentadienyl) [Ph₄C₄Si(Cl)-(Cl)SiC₄Ph₄] (<b>4</b>) with precipitation of copper metal in toluene. The green solid is suggested to be 1,1&#8242;-bissilolyl bisradical [Ph₄C₄Si-SiC₄Ph₄]^2&#8226; (<b>8</b>), and lithium cuprous chloride salts {[Li₂Cu^ICl₂]⁺&#8226;[Cu^ICl₂]^&#8722;}. Both reactions are initiated by single-electron transfer (SET) from the electron-rich anionic silole substrates (<b>1</b> and <b>3</b>) to iron(II) and copper(II).

Abstract licence: CC BY

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