Synthesis and Structure of an Extremely Air‐Stable Binuclear Hafnocene Perfluorooctanesulfonate Complex and Its Use in Lewis Acid‐Catalyzed Reactions

Abstract

Stable complexes: An extremely air-stable mu(2)-hydroxy-bridged binuclear hafonocene perfluorooctanesulfoante complex shows high catalytic efficiency in Lewis acid-catalyzed reactions, such as esterification, Friedel-Crafts acylation, the Mukaiyama aldol reation, and the allylation of aldehyde (see scheme).An extremely air-stable mu(2)-hydroxy-bridged binuclear hafonocene perfluorooctanesulfoante complex was successfully synthesized. This complex showed high catalytic efficiency in the esterification of alcohols, phenol, thiol, and amines, in the Friedel-Crafts acylation of alylaryl ethers, in the Mukaiyama aldol reaction, and in the allylation of aldehydes and could be reused.

Air-stable titanocene bis(perfluorooctanesulfonate) as a new catalyst for acylation of alcohols, phenols, thiols, and amines under solvent-free condition

“…The acidity of compounds was determined by Hammett indicators [49,50]. It was found that the complex has relatively strong acidity showing acid strength (0.8 < H 0 6 3.3; H 0 being the Hammett acidity function) stronger than that of the zirconocene and hafnocene perflouroalklysulfonates previously reported by us [44][45][46]. This result is also consistent with that determined by ESR technique in our former publication [44].…”

Synthesis and Structure of Organobismuth Chlorides and Triflates Containing (C,E)‐Chelating Ligands (E=O, S) and Their Catalytic Application in the Allylation of Aldehydes with Tetraallyltin

“…[16,17] We chose the reaction of benzaldehyde with tetraallyltin as a model. [16,17] We chose the reaction of benzaldehyde with tetraallyltin as a model.…”

Synthesis and structure of an air-stable hypervalent organobismuth (III) perfluorooctanesulfonate and its use as high-efficiency catalyst for Mannich-type reactions in water

“…Due to the stability of the cyclic frameworks, it is possible to conduct researches on the synthesis of organobismuth derivatives and to exploit the compounds for catalytic applications. On the other hand, Qiu et al postulated that the incorporation of long-chain perfluoroalkylsulfonate and perfluoroarylsulfonate groups into organometallic (e.g., Sn, Ti, Zr, Hf) complexes could result in enhanced acidity and stability of materials [13][14][15][16]. Hence, we envision that the incorporation of perfluorooctanesulfonate groups into organobismuth species can result in the generation of organobismuth compounds that are stable and have unique functionalities for catalytic reactions.…”