Reactions of N-heterocyclic ligands with substitutionally labile organometallic complexes, [(η5-C5R5)Fe(CO)2E]BF4

► Novel N-heterocyclic complexes of iron have been synthesized and characterized. ► [FpL]+ and [Fp2L]2+ (Fp = Cp(CO)2Fe; L = HMTA, DABCO) are obtained from [Fp(Et2O)]+. ► Fp∗ analogues [Fp∗L]+ and [Fp∗2L]+ (Fp∗ = Cp(CO)2Fe) are obtained from [Fp∗(THF)]+. ► [Fp(Et2O)]+ reacts with 1-methylimidazole (1-meIm) to form [Fp(1-meIm)]+. ► Similarly, 1-meIm reacts with [Fp∗(THF)]+ to yield [Fp∗(1-mIm)]+.