Abstract
The past decades have seen an explosive growth in the application of density functional theory (DFT) methods to molecular systems that are of interest in a variety of scientific fields. Owing to its balanced accuracy and efficiency, DFT plays particularly useful roles in the theoretical investigation of large molecules. Even for biological molecules such as proteins, DFT finds application in the form of, e.g., hybrid quantum mechanics and molecular mechanics (QM/MM), in which DFT may be used as a QM method to describe a higher prioritized region in the system, while a MM force field may be used to describe remaining atoms. Iron-containing molecules are particularly important targets of DFT calculations. From the viewpoint of chemistry, this is mainly because iron is abundant on earth, iron plays powerful (and often enigmatic) roles in enzyme catalysis, and iron thus has the great potential for biomimetic catalysis of chemically difficult transformations. In this paper, we present a brief overview of several recent applications of DFT to iron-containing non-heme synthetic complexes, heme-type cytochrome P450 enzymes, and non-heme iron enzymes, all of which are of particular interest in the field of bioinorganic chemistry. Emphasis will be placed on our own work.
Highlights
We present a brief overview of several recent applications of Density functional theory (DFT) to iron-containing non-heme synthetic complexes, heme-type cytochrome P450 enzymes, and non-heme iron enzymes, all of which are of particular interest in the field of bioinorganic chemistry
Density functional theory (DFT) has been playing increasingly important roles in many research activities of science and engineering in recent decades and has already become a mainstay for the quantum mechanical investigations of a broad range of complex molecular systems that are of interest in chemistry, biology, and physics (Parr and Yang, 1989; Kohn et al, 1996; Baerends and Gritsenko, 1997; Kohn, 1999; Koch and Holthausen, 2001; Zhao and Truhlar, 2008; Perdew et al, 2009; Burke, 2012; Cohen et al, 2012)
The study conducted by Hirao et al focused on the step from 4 to 7 in Scheme 6, and their comparative DFT study showed that the mechanisms involving H-abstraction from the O–H bond or from the N–H bond of 4 had low energy barriers, suggesting that the reaction proceeds via either of these mechanisms
Summary
Density functional theory (DFT) has been playing increasingly important roles in many research activities of science and engineering in recent decades and has already become a mainstay for the quantum mechanical investigations of a broad range of complex molecular systems that are of interest in chemistry, biology, and physics (Parr and Yang, 1989; Kohn et al, 1996; Baerends and Gritsenko, 1997; Kohn, 1999; Koch and Holthausen, 2001; Zhao and Truhlar, 2008; Perdew et al, 2009; Burke, 2012; Cohen et al, 2012). Previous DFT studies identified typical electron-shift patterns for the reactions of non-heme iron(IV)-oxo complexes (Figure 1B) (Hirao et al, 2006a; Shaik et al, 2007a).
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