Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds
Gil Sepulcre, Marcos (Universitat Autònoma de Barcelona. Departament de Química)
Axelson, Jordan C. (University of California. Department of Chemistry)
Aguiló Carreras, Joan (Universitat Autònoma de Barcelona. Departament de Química)
Solà-Hernández, Lluís (Universitat Autònoma de Barcelona. Departament de Química)
Francàs Forcada, Laia (Institut Català d'Investigació Química)
Poater, Albert (Universitat de Girona. Departament de Química)
Blancafort, Lluís (Institut de Química Computacional i Catàlisi)
Benet-Buchholz, Jordi (Institut Català d'Investigació Química)
Guirado López, Gonzalo (Universitat Autònoma de Barcelona. Departament de Química)
Escriche Martínez, Lluís (Universitat Autònoma de Barcelona. Departament de Química)
Llobet Dalmases, Antoni (Universitat Autònoma de Barcelona. Departament de Química)
Bofill Arasa, Roger (Universitat Autònoma de Barcelona. Departament de Química)
Sala Román, Xavier (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2016
Resum:	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. Interestingly, the aqua derivative is obtained as a pure trans-[RuII(κ-N5-bpy2PYMe)(H2O)]2+ isomer (trans-22+), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [RuII(κ-N5-bpy(bpyMe)PYMe)Cl]+ (3+) and [RuII(κ-N5-bpy(bpyMe)PYMe)(H2O)]2+ (42+) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [RuII(PY5Me2)X]n+ system (X = Cl, n = 1 (5+); X = H2O, n = 2 (62+)), which also contains a κ-N5-RuII coordination environment, and to the newly synthesized [RuII(PY4Im)X]n+ complexes (X = Cl, n = 1 (7+); X = H2O, n = 2 (82+)), which possess an electron-rich Hκ-N4C-RuII site due to the replacement of a pyridyl group by an imidazolic carbene.
Ajuts:	Ministerio de Economía y Competitividad TQ2011-26440 Ministerio de Economía y Competitividad CTQ2014-59832-JIN Ministerio de Economía y Competitividad CTQ2015-69363-P Ministerio de Economía y Competitividad CTQ2015-64261-R
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Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Publicat a:	Inorganic chemistry, Vol. 55, Issue 21 (November 2016) , p. 11216-11229, ISSN 1520-510X

DOI: 10.1021/acs.inorgchem.6b01755

Postprint 18 p, 1.2 MB

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