Modelling reaction mechanisms using density functional theory is one of the popular routes to underpin the course of a chemical reaction. Although numerous publications have come out in this area, the pitfall of modelling such reactions and explicitly publishing the entire data set (structures, energies, coordinates, spin densities, etc.) which lead to the conclusions are scarce. Here we have attempted to set a trend wherein all the computed data to underpin the reaction mechanism of ortho-hydroxylation of aromatic compounds by high-valent iron-oxo complexes ( –OOH, =O, and =O) are collected. Since the structure, energetics and other details of the calculations can be employed in future to probe/understand the reactivity pattern of such species, establishing the data set is justified. Here by analysing the presented results we also discuss in brief the presented results. 1. Introduction Heme and nonheme metal catalytic reactions of aliphatic/aromatic hydrocarbons are an important tool in pharmaceutical industry [1, 2]. Iron catalyzed hydroxylations of organic compounds have been reported by several catalysts and studied by several experimentalists and theoreticians [3–8]. The –OOH, =O, and =O species are reported to be involved in the hydroxylation of aromatic and aliphatic compounds [3, 4]. At several instances, although the presence of –OOH species has been directly detected, high-valent iron-oxo species are invoked to explain the reactivity of many mononuclear heme/nonheme iron enzymes. Particularly in the last decade the =O species are very popular as they have been hypothesized as potential oxidants in several aliphatic/aromatic hydroxylation reactions [9–13]. Besides the =O, the =O intermediates also captured attention very recently in the hydroxylation reactions [3, 4] (Figure 2). Detection of =O species under ambient conditions is a challenging task and thus this species has been detected only at a few occasions [14–16]. Of particular interest here is the recently reported ortho-hydroxylation of aromatic compounds by a putative iron(V)-oxo species [3, 4]. In this dataset paper, we aim to list all the data which are collected over the years to underpin this reaction mechanism. In our original study [17], we use [ (TPA) (CH3CN)2]2+ (tpa = tris(2-pyridylmethyl)amine) complex (shown in Figure 1) which performs ortho-hydroxylation very selectively [3]. Experimentally the mechanism of this regiospecific reaction is probed by various sets of tools such as spectroscopy and 18O labelling experiments [3]. Since hydrogen peroxide is employed as the oxidant
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