Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds
2016
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...
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