Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds
| Autor: | Xavier Sala, Marcos Gil-Sepulcre, Lluís Solà-Hernández, Laia Francàs, Antoni Llobet, Albert Poater, Jordan C. Axelson, Lluis Escriche, Lluís Blancafort, Jordi Benet-Buchholz, Joan Aguiló, Roger Bofill, Gonzalo Guirado |
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| Přispěvatelé: | Ministerio de Economía y Competitividad (Espanya) |
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Isomerization Funcional de densitat Teoria del 010405 organic chemistry Stereochemistry Ligand 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound chemistry Density functional theory Physical and Theoretical Chemistry Counterion Derivative (chemistry) Density functionals Isomerització Dichloromethane |
| Zdroj: | © Inorganic Chemistry, 2016, vol. 55, núm. 21, p. 11216-11229 Articles publicats (D-Q) DUGiDocs – Universitat de Girona instname |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.6b01755 |
| Popis: | A RuII-pentadentate polypyridyl complex [RuII(κ-N5-bpy2PYMe)Cl]+ (1+, bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6–2,2′-bipyridyl)ethane) and its aqua derivative [RuII(κ-N5-bpy2PYMe)(H2O)]2+ (22+) were synthesized and characterized by experimental and computational methods. In MeOH, 1+ exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-12+ generates a [RuIII(κ-N4-bpy2PYMe)Cl2]+ intermediate after the exchange of a pyridyl ligand by a Cl– counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-12+ is in direct equilibrium with trans-12+, with absence of the κ-N4-bis-chlorido RuIII-intermediate. All these equilibria were modeled by density functional theory calculations. Inter... |
| Databáze: | OpenAIRE |
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