An Approach to Mixed PnAsm Ligand Complexes


  • This work was supported by the Deutsche Forschungsgemeinschaft (DFG). C.S. is grateful to the Fonds der Chemischen Industrie for a Ph.D. fellowship.


The reaction of a P4 butterfly complex with yellow arsenic yields the largest mixed PnAsm ligand complexes synthesized to date. [{Cp′′′Fe(CO)2}2(μ,η1:1-P4)] reacts with As4 to yield [{Cp′′′Fe}2(μ,η4:4-PnAs4-n)] and [Cp′′′Fe(η5-PnAs5-n)]. Mass spectrometry together with NMR spectroscopy and X-ray crystallography give clear evidence about the arrangement of the E positions within the cyclo-E5 and E4 moieties of the products. Moreover, the results of DFT calculations agree well with the experimental determined outcomes. By coordinating the E4 complex [{Cp′′′Fe}2(μ,η4:4-PnAs4-n)] with CuCl, a rearrangement of the E positions occurs in favor with a preferred phosphorus coordination towards copper atoms in the resulting 1D polymeric chain.