Selective labelling of peptides using (dienyl) iron tricarbonyl cations

Dienyl cations of the type [(η5-R·C6H6)Fe(CO)3]+1 are shown to be versatile electrophilic reagents for the rapid and selective labelling of peptides and proteins, with the affinity for amino acid residues decreasing markedly in the order: cys (SH) > his (–N) > glu (δ-CO2–)≫α-NH2, lys (Iµ-NH2), ser (γ-OH), asn (-CONH)