Abstract: | The reaction of stoichiometric MeLi with the 1:1 mixture of (?5‐C5H5)Fe(CO)2I/P(OR)3 (R = Me, Et, and Ph) at ?78°C changes the bonding mode between metal and ring from (?5‐C5H5) to (?4‐exo‐MeC5H5) and the oxidation state of metal from Fe(II) to Fe(O), the novel complexes (?4‐exo‐MeC5H5)Fe(CO)2P(C)R)3 being obtained in 45‐57% yields. The reaction of trace MeLi with the 1:1 mixture of (?5‐C5H5)Fe(CO)2I/P(OMe)3 at ?78°C results in 70% yield of the phosphonate complex (?5‐C5H5)Fe(CO)2P(O)(OMe)2 which is an Arbuzov‐like dealkylation product from the cationic intermediate (?5‐C5H5)Fe(CO)2P(OMe)3+] and the iodide. The amines could assist the Arbuzov‐like dealkylation of (?5‐C5H5)Fe(CO)2P(OMe)3+] PF6?] where iron‐carbamoyl intermediates are likely involved in the case of primary amines. |