Reactions of fluorinated acid anhydrides with metal alkoxides and organometallic oxides

Abstract

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