Size-determining dependencies in supramolecular organometallic host-guest chemistry

Treatment of the pentaphosphaferrocene [Cp*Fe(η(5)-P(5))] with Cu(I) halides in the presence of different templates leads to novel fullerene-like spherical molecules that serve as hosts for the templates. If ferrocene is used as the template the 80-vertex ball [Cp(2)Fe]@[{Cp*Fe(η(5)-P(5))}(12){CuCl}(20)] (4), with an overall icosahedral C(80) topological symmetry, is obtained. This result shows the ability of ferrocene to compete successfully with the internal template of the reaction system [Cp*Fe(η(5)-P(5))], although the 90-vertex ball [{Cp*Fe(η(5):η(1):η(1):η(1):η(1):η(1)-P(5))}(12)(CuCl)(10)(Cu(2)Cl(3))(5){Cu(CH(3)CN)(2)}(5)] (2 a) containing pentaphosphaferrocene as a guest is also formed as a byproduct. With use of the triple-decker sandwich complex [(CpCr)(2)(μ,η(5)-As(5))] as a template the reaction between [Cp*Fe(η(5)-P(5))] and CuBr leads to the 90-vertex ball [(CpCr)(2)(μ,η(5)-As(5))]@[{Cp*Fe(η(5)-P(5))}(12){CuBr}(10){Cu(2)Br(3)}(5){Cu(CH(3) CN)(2)}(5)] (6), in which the complete molecule acts as a template. However, if the corresponding reaction is instead carried out with CuCl, cleavage of the triple-decker complex is found and the 80-vertex ball [CpCr(η(5)-As(5))]@[{Cp*Fe(η(5)-P(5))}(12){CuCl}(20)] (5) is obtained. This accommodates as its guest [CpCr(η(5)-As(5))], which has only 16 valence electrons in a triplet ground state and is not known as a free molecule. The triple-decker sandwich complex [(CpCr)(2)(μ,η(5)-As(5))] requires 53.1 kcal mol(-1) to undergo cleavage (as calculated by DFT methods) and therefore this reaction is clearly endothermic. All new products have been characterized by single-crystal X-ray crystallography. A favoured orientation of the guest molecules inside the host cages has been identified, which shows π⋅⋅⋅π stacking of the five-membered rings (Cp and cyclo-As(5)) of the guests and the cyclo-P(5) rings of the nanoballs of the hosts.