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Synthesis and Isomeric Analysis of Ru II Complexes Bearing Pentadentate Scaffolds.

Inorganic Chemistry 2016 November 8
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)(H2 O)]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)(H2 O)]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)(H2 O)]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 = H2 O, 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 = H2 O, n = 2 (82+ )), which possess an electron-rich κ-N4 C-RuII site due to the replacement of a pyridyl group by an imidazolic carbene.

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