A study of the structure of isomeric (eta(6)-fluoranthene)chromiumtricarbonyl complexes and interring haptotropic rearrangements in them by density functional theoryстатья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Местоположение издательства:Road Town, United Kingdom
Первая страница:244
Последняя страница:248
Аннотация:This paper presents a theoretical analysis of the structures of fluoranthene chromiumtricarbonyl complexes 1 and 2 and the mechanism of the interring haptotropic rearrangement 1 --> 2 performed using density functional theory with the nonempirically constructed PBE functional and extended split basis sets. The reaction paths were calculated for the interring haptotropic rearrangement and rotations of the metalcarbonyl fragment in the regioisomeric complexes, and the structures and energy characteristics of all stationary points of the system were determined. The migration of the metalcarbonyl group was shown to occur at the periphery of the ligand via transition states with the structure of eta(4)-trimethylmethane complexes. A high-energy local minimum corresponding to the eta(5) intermediate with the coordination of Cr(CO)(3) to the five-membered fluoranthene ring was also found on the potential energy surface of the system. The calculated geometric parameters of 1 and 2 and the activation barriers were in close agreement with experimental data. The structures and energies of fluoranthene complexes with the electron-deficient [(CH3CN)Cr(CO)(3)] fragment, which model the intermediates of the last step of the reaction between fluoranthene and (CH3CN)(3)Cr(CO)(3), were calculated to show that the predominant formation of complex 1 in this reaction under kinetic control conditions was determined by its origination from stabler precursors with the coordination of the chromium atom to the naphthalene and central five-membered fragments.