Anion templated synthesis of Ni/Pd containing metalla-macrocycles

The anion templated synthesis of the nickel/palladium-based metalla-macrocycles [Pd2Ni2(atu)(4)(PPh3)(4)X](3+) (X=Cl, 1; Br, 2; I, 5; atu=deprotonated amidinothiourea) is reported. In the presence of other anions such as CF3SO3- or NO3- the formation of the simple complex Pd(Hatu)X-2 (X=CF3SO3- or NO3-) is observed. Structural characterisation of two of the mixed-metal compounds (1 and 2, where X=Cl and Br respectively) confirmed square arrangements for the metalla-macrocycles and revealed some interesting features in the molecular structure of the species. The encapsulated anions inside the metalla-macrocycles have been demonstrated to be mobile in solution and halide exchange reactions have been carried out.