Chemical design of heterometallic carboxylate structures with Fe3+ and Ag+ ions as a rational synthetic approach

Solid phase thermolysis of pivalate complex [Fe₃O(Piv)₆(HPiv)₃]Piv generates the [Fe₃O(Piv)₆]⁺ complex cation due to a deficiency of ligands in the coordination sphere of the metal ions. Crystallization of [Fe₃O(Piv)₆]⁺ from THF–EtOH leads to the heteroleptic complex [Fe₃O(Piv)₆(THF)(EtOH)(OH)] · 0.5 THF · 0.5 H₂O in 69% yield, while the reaction of [Fe₃O(Piv)₆]⁺ with AgNO₃ in toluene results in the complex [Fe₄Ag₄O₂(Piv)₁₂] · 2 PhMe with a rare combination of Fe^III and Ag^I atoms. Crystal structures of the two new complexes have been established.