First diphosphinoamine ligand bearing a polymerizable side chain: Complexation with copper(I)

A diphosphinoamine ligand with a polymerizable side chain, (PPh 2 ) 2 NCH 2 C 6 H 4 CHCH 2 (vbzpnp or 1 ), was synthesized. The ligand could be polymerized by anionic polymerization with n ‐butyllithium as the initiator. Polyvbzpnp was soluble in tetrahydrofuran and chloroform but was insoluble in methanol and was characterized with NMR, IR, and gel permeation chromatography. The number‐average and weight‐average molecular weights were 40,050 and 55,690, respectively, and the polydispersity index was 1.39. [Cu(CH 3 CN) 4 ]ClO 4 formed a bischelated complex with the monomer and produced [Cu( 1 ) 2 ]ClO 4 ( 2 ), and CuCl formed a tetramer, Cu 4 ( 1 ) 2 Cl 4 ( 3 ). All the compounds ( 1 , 2 , and 3 ) were characterized with single‐crystal‐structure determination, NMR, and IR spectroscopy. The addition of [Cu(CH 3 CN) 4 ]ClO 4 to polyvbzpnp resulted in an insoluble crosslinked polymer, which was characterized with solid‐state 31 P { 1 H} magic‐angle‐spinning NMR. The copolymerization of styrene and 1 produced a styrene–vbzpnp copolymer that was found to be soluble in common organic solvents. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3411–3420, 2005