Correlation between computed gas-phase and experimentally determined solution-phase infrared spectra: Models of the iron–iron hydrogenase enzyme active site

Abstract

Gas-phase density functional theory calculations (B3LYP, double zeta plus polarization basis sets) are used to predict the solution-phase infrared spectra for a series of CO- and CN-containing iron complexes. It is shown that simple linear scaling of the computed CO and CN stretching frequencies yields accurate predictions of the the experimentally determined ν(CO) and ν(CN) values for a variety of complexes of different charges and in solvents of varying polarity. As examples of the technique, the resulting correlation is used to assign structures to spectroscopically observed but structurally ambiguous species in two different systems. For the (μ-SCH₂CH₂CH₂S)[Fe(CO)₃]₂ complex in tetrahydrofuran solution, our calculations show that the initial electrochemical reduction process leads to a simple one-electron reduced product with a structure very similar to the (μ-SCH₂CH₂CH₂S)[Fe(CO)₃]₂ parent complex. For the iron–iron hydrogenase enzyme active site, our computations show that the absence or presence of a water molecule near the distal iron center (the iron center further from the [4Fe4S] cluster and protein backbone) has very little effect on the predicted infrared spectra. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1454–1462, 2006