Friedel–Crafts functionalization of the cyclopentadienyl ligand in buckymetallocenes

Abstract

Acylated buckyferrocene and ruthenocene, Fe(η⁵-C₆₀Me₅)(η⁵-C₅H₄COR) (R = Me, Ph, and CHCHPh) and Ru(η⁵-C₆₀Me₅)(η⁵-C₅H₄COR) (R = Me and Ph), were obtained by Friedel–Crafts acylation of the parent buckymetallocenes with the corresponding acid chlorides and aluminum chloride in carbon disulfide at ambient temperature. The electron withdrawing and sterically hindered nature of the acyl groups were revealed by X-ray crystallography, infrared spectroscopy and electrochemical measurements. The possibility of further derivatizing the acylated products was illustrated by the conversion of the acetyl buckyruthenocene into the corresponding hydroxy and acetoxy compounds Ru(η⁵-C₆₀Me₅)(η⁵-C₅H₄CH(OH)Me) and Ru(η⁵-C₆₀Me₅)(η⁵-C₅H₄CH(OAc)Me).