DFT study of chromium tricarbonyl complexes of coronene and kekulene

• Published in: Moscow University chemistry bulletin 2017-09, Vol.72 (5), p.201-211
• Main Authors: Zhulyaev, N. S., Gloriozov, I. P., Oprunenko, Yu. F., Saillard, J.-Y.
• Format: Article
• Language: English
• Subjects: Barriers; Catalysis; Chemical Sciences; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Density functional theory; Hydrocarbons; Naphthalene; Polycyclic aromatic hydrocarbons; Potential energy; Quantum chemistry; Tricarbonylchromium
• ISSN: 0027-1314; 1935-0260
• DOI: 10.3103/S0027131417050091

A quantum chemical study of the mechanism and determination of the activation barriers of intramolecular η 6 ,η 6 -inner-ring haptotropic rearrangements (IHR), consisting in moving a chromium tricarbonyl group Cr(CO) 3 from one six-membered aromatic ring to another, are carried out using the density functional theory (DFT) for the respective η 6 -complexes of coronene I and kekulene II. The stationary states on the potential energy surface, determining the mechanism of η 6 ,η 6 -IHR, have a lower hapticity, which is of interest for catalysis because of the possibility of coordinating an additional substrate and reagent around the transition metal during the rearrangement. The processes of η 6 ,η 6 -IHR complexes I and II occur with similar energy barriers (ΔG ≠ ≈ 20–25 kcal/mol) that are lower than the barriers (ΔG ≠ ≈ 30 kcal/mol) of similar transformations previously calculated or measured for naphthalene complexes and a number of small polyaromatic hydrocarbons.