Thermolysis of [CpMn(η(6)-cht)] with P4 in 1,3-diisopropylbenzene leads to the formation of the heterocubane [Cp4Mn4P4] () in high yields, as a rare example of 'naked' phosphorus containing complexes of manganese. Compound 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 can be addressed for a coordination towards cymantrene resulting in [{(CpMn)4(μ3-P)4}{CpMn(CO)2}n] (: n = 1; : n = 2; : n = 3; : n = 4), and shows that is a tetra-topic building block in coordination chemistry.
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