Synthesis and Isomeric Analysis of RuII Complexes Bearing Pentadentate Scaffolds

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 κ-N4C–RuII site due to the replacement of a pyridyl group by an imidazolic carbene.