P-Fluorous Phosphines as Electron-Poor/Fluorous Hybrid Functional Ligands for Precious Metal Catalysts: Synthesis of Rh(I), Ir(I), Pt(II), and Au(I) Complexes Bearing P-Fluorous Phosphine Ligands

Abstract

P-Fluorous phosphine (R 2 PR f ), in which the perfluoroalkyl group is directly bonded to the phosphorus atom, is a promising ligand because it has a hybrid functionality, i.e., electron-poor and fluorous ligands. However, examples of P-fluorous phosphine-metal complexes are still rare, most probably because the P-fluorous group is believed to decrease the coordination ability of the phosphines dramatically. In contrast, however, we have succeeded in synthesizing a series of P-fluorous phosphine-coordinated metal complexes such as rhodium, iridium, platinum, and gold. Furthermore, the electronic properties of R 2 P n C 10 F 21 are investigated by X-ray analysis of PtCl 2 (Ph 2 P n C 10 F 21 ) 2 and the infrared CO stretching frequency of RhCl(CO)(R 2 P n C 10 F 21 ) 2 . IrCl(CO)(Ph 2 P n C 10 F 21 ) 2 -and AuCl(R 2 P n C 10 F 21 )-catalyzed reactions are also demonstrated.

Phosphorus-Recycling Wittig Reaction: Design and Facile Synthesis of a Fluorous Phosphine and Its Reusable Process in the Wittig Reaction

“…We previously developed a P -fluorous phosphine 1 as a recoverable and reusable ligand for transition-metal-catalyzed cross-coupling reactions. − P -Fluorous phosphine 1 , in which the perfluoroalkyl group (R f ) is directly bound to the phosphorus atom, is prepared and its fluorous affinity enables the reuse of 1 /palladium­(II) complexes using a fluorous biphasic system (FBS) …”