Random Copolymers with 2,2′-Dioxy-1,1′-biphenyl-phosphazene and Chiral 2,2′-dioxy-1,1′-binaphthylphosphazene Units Functionalized in the 6,6′-Positions with PPh2 Groups as Precursors for Ru(arene) Catalysts

Abstract

The chiral phosphazene copolymers {[NP(O2C12H8)]0.9[NP(O2C20H12)]0.1} (1) and {[NP(O2C12H8)]0.9[NP(O2C20H10Br2)]0.1} n (2) [(O2C12H8) = 2,2′-dioxy-1,1′-biphenyl; (O2C20H12) = R-2,2′-dioxy-1,1′-binaphthyl and (O2C20H10Br2) = R-6,6′-dibromo-2,2′-dioxy-1,1′-binaphthyl] were prepared by sequential substitution from [NPCl2] n and the corresponding dihydroxy-biphenyl or binaphthyl reagents in the presence of Cs2CO3 and K2CO3. The reaction of (2) with tBuLi in THF, followed by addition of PPh2Cl and a treatment with SiHCl3/PPh3 to eliminate any oxidized OC6H4P(O)Ph2 groups, gave the phosphine containing copolymer {[NP(O2C12H8)]0.9[NP(O2C20H10[PPh2]2)]0.1} n (3), that was used as a chiral ligand to support [Ru(p-cymene)Cl] complexes. The resulting catalyst was active for hydrogen transfer from isopropyl alcohol to acetophenone but the placement of the Ru centers in the 6,6′-positions of the binaphthoxyphosphazene units induced no enantioselectivity.