The catalytic activity of cyclophosphazenic polypodands 1a-c was evaluated in typical reactions performed under solid-liquid (SL) and liquid-liquid (LL) phase-transfer catalysis (PTC) conditions. Such activity is largely determined by the complexation extent of 1a-c which is in turn related to the number of binding sites of the ligand (1a< 1b⩽ 1c) and to the nature of the inorganic salt M+ Y−(Na+> K+ 2> Rb+ and SCN−∼ I−> Br−). Also the ...