Synthesis and characterization of manganese triple-decker complexes

The use of the highly sterically demanding Cp^BIG ligand (Cp^BIG = C₅(4-nBuC₆H₄)₅) and white phosphorus (P₄) enables the synthesis of new P-rich derivatives of the rare P_n ligand complexes of manganese. The obtained complexes, [{Cp^BIGMn}₂(μ,η^5:5-P₅)] (2) and [{Cp^BIGMn}₂(μ,η^2:2-P₂)₂] (3), exhibit the highest number of P atoms in this class of manganese compounds identified by X-ray structure analyses. The EPR spectrum of the 29 VE triple-decker complex 2 shows one unpaired electron coupling with two 5/2 spin Mn nuclei.