Abstract. Gas phase studies offer an ideal medium whereby structural and reactivity properties of charged species may be unveiled in the absence of solvent, matrix or counterion effects. In this environment NO binds to iron(II)-and iron(III)-hemes with comparable kinetics and equilibrium parameters, conclusively elucidating the factors determining the widely different affinity in protic solvents or in heme proteins. IRMPD spectroscopy of the isolated species provides unambiguous characterization of the gaseous nitrosyl heme complexes.