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A density functional study of intra- and interring haptotropic eta(2),eta(2) rearrangements in rhodium, ruthenium, and osmium naphthalene complexesстатья
Информация о цитировании статьи получена из
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Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Oprunenko Yu F., Gloriozov I.P.
- Журнал: Russian Journal of Physical Chemistry A
- Том: 86
- Номер: 6
- Год издания: 2012
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 979
- Последняя страница: 986
- DOI: 10.1134/S0036024412060209
- Аннотация: The density functional theory method was used to perform quantum-chemical modeling of the mechanisms of eta(2),eta(2)-intraring (Intra-HR) and eta(2),eta(2)-interring (Inter-HR) haptotropic rearrangements for mu(2) complexes of naphthalene with rhodium, ruthenium, and osmium. The structure of transition states and intermediates was studied, and the energy parameters of haptotropic rearrangements in these complexes were determined. We used the PBE functional, the TZV2p three-exponential basis set for valence electrons, and the SBK-JC relativistic pseudopotential for core electrons. eta(2),eta(2) Intra-HR was found to occur inside the aromatic ring of eta(2) naphthalene complexes without going outside it through intermediates and transition states with eta structures ( = 1, 2). Inter-HR occurred as metal replacements on the periphery of the naphthalene ligand through intermediates and transition states with eta structures ( = 1, 2, 3) from one ring into another. The calculated activation barriers for eta(2),mu(2) Intra-HR and eta(2),eta(2) Inter-HR in the complexes studied closely agree with their experimental values.
- Добавил в систему: Опруненко Юрий Федорович