Complete Mechanism of σ* Intramolecular Aromatic Hydroxylation through O₂Activation by a Macrocyclic Dicopper(I) Complex

Abstract

The present study reports the first example of a complete and detailed mechanism of intramolecular aromatic hydroxylation through O(2) activation by a hexaazamacrocyclic dicoppper(I) complex, [Cu(I)(2)(H3m)](2+). The reactivity of this complex has been previously studied experimentally, although only the characterization of the final mu-phenoxo-mu-hydroxo [Cu(II)(2)(H3m-O)(mu-OH)](2+) product was possible. In the present theoretical study, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, that is, from the initial reaction of O(2) with the dicopper(I) species to the final [Cu(II)(2)(H3m-O)(mu-OH)](2+) product using the B3LYP method. Our results indicate that a Cu(I)Cu(II)-superoxo species is formed first, then the interaction of the O(2) moiety with the second Cu(I) center leads to a mu-eta(2):eta(2)-peroxo-Cu(II)(2) intermediate. This latter species is found to be close in energy with the isomeric bis(mu-oxo) species. The relative stability of these two isomers depends on the method of calculation, and therefore, it has not been possible to reach a definite conclusion about the nature of the active species in this reaction mechanism. Notwithstanding, our B3LYP calculations indicate that it is the mu-eta(2):eta(2)-peroxo species that evolves via an electrophilic sigma* attack involving a concerted peroxide O-O bond cleavage and C-O bond formation to a Wheland-type intermediate. The reaction follows with a proton release assisted by the presence of a second aromatic ring yielding a mu-hydroxo-mu-oxo intermediate species, which, in the final stage of the reaction, rearranges to the product. The proton transfer path points out the possibility to design new systems with improved reactivity by properly placing a second aromatic ring to assist the deprotonation step. The lack of high energy barriers and deep energy wells explains the difficulty to trap intermediates experimentally.

Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper(I) complex

“…1). The results are compared with those obtained in a similar previous study in which the hexaazamacrocyclic ligand used (H3m) was more flexible [40]. Crystallographic data on related copper compounds by using the same ligand suggest that complex a may present many conformations of rather similar energy [47]; however, the optimized geometries of similar complexes was found to be in perfect agreement with the X-ray structures [40,48–56].…”

“…All geometry optimizations, as described in [40], were performed with the Gaussian03 package [57], by using the B3LYP functional [58–60] and the standard 6-31G(d) basis set [61–62]. The geometries obtained at the B3LYP/6-31G(d) level were used to perform single-point energy calculations with a larger basis set, the 6-311G(d,p) basis set [63], and the same functional (B3LYP/6-311G(d,p)//B3LYP/6-31G(d)).…”

Deactivation of Ru-benzylidene Grubbs catalysts active in olefin metathesis

“…Although the optimization suffered the simplification of the tricyclohexyl phosphine by trimethyl phosphine, the agreement was excellent, with a rmsd of 0.039 Å for distances and of 0.9°for angles [53][54][55]. 1 This indicates that the sterically demanding PCy 3 phosphine can be replaced with the less bulkier PMe 3 phosphine to shed light on this kind of reactions.…”

Crystal structure of aqua(perchlorato)bis[μ-(E)-2-({[2-(pyridin-2-yl)ethyl]imino}methyl)phenolato-κ4N,N′,O:O]dicopper(II) perchlorate

“…Proteins containing dinuclear copper centers play important roles in biology, including dioxygen transport or activation, electron transfer, reduction of nitrogen oxides and hydrolytic chemistry (Karlin & Tyeklar, 1993;Torelli et al, 2000;Poater et al, 2008;Utz et al, 2003). The catalytic properties of some dicopper complexes have also been observed in some recent studies (Jagoda et al, 2005).…”