Anion templated synthesis of Ni/Pd containing metalla-macrocycles

Abstract

The anion templated synthesis of the nickel/palladium-based metalla-macrocycles [Pd₂Ni₂(atu)₄(PPh₃)₄X]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)X₂ (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.