A diphosphinoamine ligand with a polymerizable side chain, (PPh2)(2)N-CH2-C6H4-CH=CH2 (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(CH3CN)(4)]ClO4 formed a hischelated complex with the monomer and produced ECU(1)(2)]ClO4 (2), and CuCl formed a tetramer, Cu-4(1)(2)Cl-4 (3). All the compounds (1, 2, and 3) were characterized with single-crystalstructure determination, NMR, and IR spectroscopy. The addition of [Cu(CH3CN)(4)]ClO4 to polyvbzpnp resulted in an insoluble crosslinked polymer, which was characterized with solid-state P-31 {H-1} 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. (c) 2005 Wiley Periodicals, Inc.