|
ИСТИНА |
Войти в систему Регистрация |
ИПМех РАН |
||
Ion Pairing in Inter-Ring Haptotropic Rearrangements in Cationic Cyclopentadienyl Complexes of Ruthenium with Naphthalene: A DFT Investigationстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 14 сентября 2013 г.
- Авторы: Fetisov E.O., Gloriozov I.P., Oprunenko Yu F., Saillard J.Y., Kahlal S.
- Журнал: Organometallics
- Том: 32
- Номер: 12
- Год издания: 2013
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 3512
- Последняя страница: 3520
- DOI: 10.1021/om4003335
- Аннотация: DFT calculations have been performed on the naphthalene cationic complex eta(6)-C10H8RuCp+ in the presence of different anions. In a first step, geometry optimization of the PF6- salt carried out in the presence of 15 solvent molecules for 3 different solvents (methylene chloride, acetone, and water) indicated that ion pairing occurs in the less polar methylene chloride solvent, whereas the ions are separated in the more polar acetone and water. In a subsequent step, the inter-ring haptotropic rearrangement (IRHR) of eta(6)-C10H8RuCp+ has been modeled both as an isolated cation (separated ion pairs (SIP)) and in the presence of a counterion (contact ion pair (CIP)). The IRHR activation barrier is found to be much lower in the CIP case due to the cation-anion interaction, which tends to reduce the metal unsaturation during the process. The size of the anion is also important. Small anions such as BF4- favor lower barriers. These results should also hold for photochemically induced IRHR processes, since the SIP mechanism involves structurally similar intermediates and transition states.
- Добавил в систему: Глориозов Игорь Павлович