Air-stable μ2-hydroxyl bridged cationic binuclear complexes of zirconocene perfluorooctanesulfonates: their structures, characterization and application

Abstract Three air-stable zirconocene perfluoro-octanesulfonates were successfully synthesized by treatment of C 8 F 17 SO 3 Ag with (RCp) 2 ZrCl 2 [R = H, n -Bu, t -Bu]. According to X-ray analysis, they have μ 2 -hydroxyl bridged cationic binuclear structures: ( i ) [CpZr(OH 2 ) 3 ] 2 ( μ 2 -OH) 2 (OSO 2 C 8 F 17 ) 4 ·2THF·4H 2 O ( 1a ·2THF·4H 2 O), ( ii ) [ n -BuCpZr(OH 2 ) 3 ] 2 ( μ 2 -OH) 2 (OSO 2 C 8 F 17 ) 4 ·6H 2 O ( 2a ·6H 2 O), and ( iii ) [ t -BuCpZr(OH 2 ) 3 ] 2 ( μ 2 -OH) 2 (OSO 2 C 8 F 17 ) 4 ·2C 3 H 6 O·8H 2 O ( 3a ·2C 3 H 6 O·8H 2 O). The ligands of water and organic molecules in the complexes originated from the moist air and solvent during their recrystallization. These complexes were characterized with different techniques, and found to show water tolerance, air/thermal stability as well as strong Lewis acidity. Moreover, the complexes showed highly catalytic activity in various reactions of C C bond formation. With good recyclability, they should find wide applications in organic chemistry.