Triphenylphosphine‐functionalized core‐cross‐linked micelles and nanogels with a polycationic outer shell: synthesis and application in rhodium‐catalyzed biphasic hydrogenations

Hui Wang (1) , Lorenzo Vendrame (1) , Christophe Fliedel (1) , Si Chen (1) , Florence Gayet (1) , Franck d'Agosto (2) , Muriel Lansalot (2) , Eric Manoury (1) , Rinaldo Poli (1, 3)

1 LCC - Laboratoire de chimie de coordination
2 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
3 IUF - Institut universitaire de France

Unimolecular amphiphilic nanoreactors with a poly(4‐vinyl‐N‐methylpyridinium iodide) (P4VPMe+I‐) polycationic outer shell and two different architectures (core‐crosslinked micelles, CCM, and nanogels, NG), with narrow size distributions around 130‐150 nm in diameter, were synthesized by RAFT polymerization from an R0‐4VPMe+I‐140‐b‐S50‐SC(S)SPr macroRAFT agent by either chain extension with a long (300 monomer units) hydrophobic polystyrene‐based block followed by crosslinking with diethylene glycol dimethacrylate (DEGDMA) for the CCM particles, or by simultaneous chain extension and crosslinking for the NG particles. A core‐anchored triphenylphosphine (TPP) ligand functionality was introduced by using 4‐diphenylphosphinostyrene (DPPS) as a comonomer (5‐20% mol/mol) in the chain extension (for CCM) or chain extension/crosslinking (for NG) step. The products were directly obtained as stable colloidal dispersions in water (latexes). After loading with [RhCl(COD)]2 to yield [RhCl(COD)(TPP@CCM)] or [RhCl(COD)(TPP@NG)], respectively, the polymers were used as polymeric nanoreactors in the Rh‐catalyzed aqueous biphasic hydrogenation of the model substrates styrene and 1‐octene, either neat (for styrene) or in an organic solvent (toluene or 1‐nonanol). All hydrogenations were rapid (TOF up to 300 h‐1 ) at 25°C and 20 bar of H2 pressure, the biphasic mixture rapidly decanted at the end of the reaction (< 2 min), the Rh loss was negligible (<0.1 ppm in the recovered organic phase), and the catalyst phase could be recycled 10 times without significant loss of catalytic activity.

Mots clés: Polyelectrolyte; RAFT polymerization; Polymerization-induced self-assembly; Poly(1-methyl-4-vinylpyridinium iodide); Catalytic nanoreactors

Domaines: Chimie de coordination

Hui Wang, Lorenzo Vendrame, Christophe Fliedel, Si Chen, Florence Gayet, et al.. Triphenylphosphine‐functionalized core‐cross‐linked micelles and nanogels with a polycationic outer shell: synthesis and application in rhodium‐catalyzed biphasic hydrogenations. Chemistry - A European Journal, 2021, 27 (16), pp.5205-5214. ⟨10.1002/chem.202004689⟩. ⟨hal-03081418⟩