The synthesis of the cluster complexes [(Cp'''Co)3(µ3,η2:η2:η2-E3)(µ3-E)] (E = P (3), As (4)) starting from the anionic triple-decker complexes [K(18cr6)(dme)2][(Cp'''Co)2(µ,η4:η4-E4)]- (E = P (1), As (2)) by electrophilic quenching with the Co dimer [(Cp'''CoCl)2] is reported. Both complexes show a distinct redox chemistry, which was first investigated by cyclic voltammetry. Subsequently, the monoanions [K(L)(sol)n][(Cp'''Co)3(µ3,η2:η2:η2-E3)(µ3-E)] (E = P, L = 18cr6, sol = dme, n = 2 (5), E = As, L = 2,2,2-crypt, n = 0 (6)), the monocations [(Cp'''Co)3(µ3,η2:η2:η2-E3)(µ3-E)][FAl] (E = P (7), As (8)) and the dications [(Cp'''Co)3(µ3,η3:η3:η3-E4)][TEF]2 (E = P (9), As (10)) could be realized experimentally and isolated in moderate to good yields. All compounds were characterized by single crystal X-ray structure analysis, NMR and EPR spectroscopy, mass spectrometry and elemental analysis.
Keywords: arsenic * cluster * cobalt * phosphorus * redox chemistry.
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