A Muhieddine, S Soorkia, J Attard, A de La Lande, Niloufar Shafizadeh, B Soep. J. Phys. Chem. A, 2025, 129, 7087–7093. DOI: doi.org/10.1021/acs.jpca.5c02554

The ligation of 4-coordinated ferrous heme has been investigated in the gas phase using singly deprotonated heme anions to act as a model for neutral heme. The equilibrium of dioxygen and carbon monoxide ligated to deprotonated heme was observed in the 250–150 K temperature range in a Paul ion trap. The van’t Hoff equation was used for the determination of ligand binding energies with CO or O₂. Density functional theory calculations have been undertaken to analyze the mechanism of bonding that evolves through spin-orbit crossing between the triplet heme reactant and the singlet carbon monoxide-ligated product. The deprotonated heme anion is a good model for neutral heme, since the negative charge on the carboxylate end of the propionate group of heme is shown to have little influence. Deprotonated heme anions yield a ligation enthalpy of 4-coordinated heme with O₂ or CO, which is surprisingly low (respectively, ΔH = 20.6 ± 1.7 and 37.9 ± 1.6 kJ mol¹).