Density functional characterization of the chemoselective oxidation of catechol by using molecular oxygen: thermodynamics of the reaction between [(triphos)Ir(dtbc)]+ and O2.

The catalytic mechanism of intra and extra catechol cleaving dioxygenases is still a matter of debate, because the intermediate transient oxygen adduct has never been isolated in these enzymes. The complex [(triphos)Ir(dtbc)](+) (triphos=MeC(CH(2)PPh(2))(3), DBTC(2-)=3,5-di-tert-butylcatecholate), reacts with molecular oxygen and exhibits a ring-cleaving catalytic activity, and a stable oxygen intermediate appears; this stimulates an opportunity for obtaining information that can be transferable to the above-mentioned enzymatic catalytic centers, therefore, giving a breakthrough into the strategy of oxygen activation in these natural systems. Here, we present the results of our computational approach, based on density functional theory, focusing on the following aspects: to explain the interaction with molecular oxygen and how to avoid the existing spin problem, to understand the formation of the bridging moiety, to clarify, if any, the possible influence on the structure of the formed adduct of the bidentate versus monodentate binding of the catechol ligand, and to disclose, eventually, the nature of final decomposition products with the aim to rationalize the intra versus extra cleavage of the catechol molecule itself.