Reactions of fluorinated acid anhydrides with metal alkoxides and organometallic oxides

Abstract Reactions of (CF 3 CO) 2 O, (CF 3 SO 2 ) 2 O and (FSO) 2 O with Zr(OCH 3 ) 4 at elevated temperatures resulted in the isolation of mixed ligand derivatives Zr(OCH 3 ) 2 (O 2 CCF 3 ) 2 , Zr(OCH 3 ) 2 (O 3 SCF 3 ) 2 and Zr(OCH 3 ) 2 (O 3 SF) 2 , respectively. However, reactions of these fluorinated acid anhydrides with Zr(OC 2 H 5 ) 4 yielded previously known tetrakis derivatives Zr(O 2 CCF 3 ) 4 , Zr(O 3 SCF 3 ) 4 and Zr(O 3 SF) 4 in quantitative yields. These fluorinated acid anhydrides react with φ 3 SbO at ambient temperature to produce φ 3 SbX 2 derivatives (X = CF 3 COO,SO 3 CF 3 or SO 3 F) in quantitative yields. This is a fairly convenient route to prepare organometallic fluorosulfates which substantiates the potentiality of S 2 O 5 F 2 as a fluorosulfonating agent. The utility of such reactions and some reactions of (CF 3 CO) 2 O, (SO 2 CF 3 ) 2 O and (SO 2 F) 2 O with [Cp 2 TiCl] 2 O and [CP 2 ZrCl] 2 O leading to the isolation of novel or previously known compounds will be discussed.