Structural Characterization of Bismuth(III) and Antimony(III) Chlorotriflates: Key Intermediates in Catalytic Friedel−Crafts Transformations

✍ Scribed by Stéphane Mazières; Christophe Le Roux; Magali Peyronneau; Heinz Gornitzka; Nicolas Roques

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 119 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400281

✦ Synopsis

Abstract

Chlorotriflates of antimony and bismuth Cl~n~M(OSO~2~CF~3~)~3−~~n~ (n = 1 or 2) are believed to be metallic intermediates of major importance in Friedel−Crafts reactions that use Bi(OSO~2~CF~3~)~3~, Sb(OSO~2~CF~3~)~3~, the systems BiCl~3~/CF~3~SO~2~OH or SbCl~3~/CF~3~SO~2~OH as catalysts. Unknown until now, the compounds ClBi(OSO~2~CF~3~)~2~ (1) and Cl~2~Sb(OSO~2~CF~3~) (2) have been synthesized by reaction of MCl~3~ (M = Bi, Sb) with triflic acid. After crystallization from THF, 1 and 2 were investigated in the solid state by X‐ray crystallography. Their use as catalysts in benzoylation of toluene, acylation of m‐xylene, and sulfonylation of toluene led to conclusive results, thus giving weight to their key role as intermediates in Friedel−Crafts reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)