Elucidating the effect of the ionic liquid type and alkyl chain length on the stability of ionic liquid-iron porphyrin complexes

The present study is motivated by the long-term objective of understanding how ionic liquids are biodegraded by cytochrome P450, which contains iron porphyrin (FeP) serving as the catalytic center. To this end, the current study is designed to elucidate the impact of types and conformations of ionic liquids on the binding energy with FeP, the key interactions that stabilize the ionic liquid-FeP complex, and how the electron uptake ability of FeP is altered in the presence of ionic liquids. Four classes of ionic liquids are considered: 1-alkyl-3-methylimidazolium, 1-alkyl-pyridinium, 1-alkylsulfonium, and N-methyl-N-alkylpyrrolidinium. The influence of linear alkyl chains of ethyl, butyl, hexyl, octyl, and decyl is examined on the favorable binding modes with FeP, considering two widely different conformations: tail up and tail down with respect to FeP. Electronic structure calculations are performed at the M06 level of theory with the 6-31G(d,p) basis set for C, H, and N atoms, while the Lanl2DZ basis set is employed for Fe. Donor-acceptor interactions contributing to the binding of ionic liquids to FeP are unraveled through the natural bond orbital analysis. The results from this study indicate that the binding energies are dependent not only on the class of ionic liquids but also on the conformations presented to FeP. The propensity of FeP to acquire an electron is significantly enhanced in the presence of ionic liquid cations, irrespective of the type and the alkyl chain length.