The synthesis of the heterocubane cluster [{CpMn}4(μ3-P)4] as a tetrahedral shaped starting material for the formation of polymeric coordination compounds

Abstract

Thermolysis of [CpMn(η⁶-cht)] with P₄ in 1,3-diisopropylbenzene leads to the formation of the heterocubane [Cp₄Mn₄P₄] (1) in high yields, as a rare example of ‘naked’ phosphorus containing complexes of manganese. Compound 1 is characterized and studied by DFT calculations and reflection measurements. 1D coordination polymers [{(CpMn)₄(μ₃-P)₄}(CuX)]_n (2-Cl: X = Cl; 2-Br: X = Br) are obtained in the reaction with CuX. Furthermore, it is shown that all four P atoms in 1 can be addressed for a coordination towards cymantrene resulting in [{(CpMn)₄(μ₃-P)₄}{CpMn(CO)₂}_n] (3a: n = 1; 3b: n = 2; 3c: n = 3; 3d: n = 4), and shows that 1 is a tetra-topic building block in coordination chemistry.