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

The reaction of the polyphosphazenes {[NP(O2C12H8)]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 metal-organic 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).