Designed synthesis of metal-organic frameworks containing gold(I) cations supported in phosphazene-phosphine polymeric matrices

The reaction of the polyphosphazenes {[NP(O2C12 H-8)](1) (x)[NP(OC6H4PPh2)(2)](x)}(n), x = 0.15 (1a), 0.25 (1b), 0.35 (1c), with [Au(THT)Cl] (THT = tetrahydrothiophene) in dichloromethane gave the polymers {[NP(O2C12H8)](1) (x)[NP(OC6H4PPh2AuCl)(2)](x)}(n), x = 0.15, (2a), 0.25 (2b), 0.35 (2c), respectively. The reaction of (1a) with [Au(PPh3)(2)]PF6 in refluxing THF led to the replacement of the PPh3 ligands giving a metalorganic framework of idealized formula {[NP(O2C12H8)](1) (x)[NP(OC6H4PPh2)(2)(AuPF6)(0.5)](x)}(n), x = 0.15, (3a), 0.25 (3b) containing cationic [-Ph2P-Au+-PPh2-] cross-linking sites. The insoluble polymeric matrix (3a), having pendant PPh2 groups, was reacted with [Au(THT)Cl] to give the new polymeric framework of composition {[NP(O2C12H8)](0.85)[NP(OC6H4PPh2)(2)(AuPF6)(0.5)(AuCl)(0.5)](0.15)}(n)(4). (C) 2008 Elsevier B. V. All rights reserved.