Influence of Ion Pairing in Inter-Ring Haptotropic Rearrangements in Cationic Cyclopentadienyl Complexes of Ruthenium with Naphthalene: A DFT Investigation
| Autor: | Igor P. Gloriozov, Samia Kahlal, Jean Yves Saillard, Evgenii O. Fetisov, Yu. F. Oprunenko |
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| Rok vydání: | 2013 |
| Předmět: |
chemistry.chemical_classification
Organic Chemistry Cationic polymerization chemistry.chemical_element Photochemistry Chloride Ion Ruthenium Inorganic Chemistry Solvent chemistry.chemical_compound chemistry Cyclopentadienyl complex medicine Physical and Theoretical Chemistry Methylene Counterion medicine.drug |
| Zdroj: | Organometallics. 32:3512-3520 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | DFT calculations have been performed on the naphthalene cationic complex η6-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 η6-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 mec... |
| Databáze: | OpenAIRE |
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