abstract
Several ruthenium(II)-chloro-dimethylsulfoxide complexes with formulae [RuCl2(DMSO)(k(3)-L-1)] or [RuCl(DMSO)(k(4)-L-2)](+), where L-1=[9]aneS(3) (2) or ttbt (5) and L-2=[12]aneS(4) (3), [14]aneS(4) (4) or [14]aneN(4) (6), have been synthesized from cis,fac-[RuCl2(S-DMSO)(3)(O-DMSO)] (1) and the respective macrocycle. They were spectroscopically characterized by FT-IR, FT-Raman, NMR, and UV/Vis. Particular attention was given to fac-[RuCl2(DMSO)(k(3)-ttbt)] (5), the first octahedral complex of ttbt, which was also studied by DFT calculations. The behavior of the complexes in coordinating solvents water, acetonitrile, and dimethylsulfoxide was studied to understand their reactivity and predict the resulting ions formed in solution. The role of the counter ion (Cl(-)vs. ) was also evaluated. The results indicate that the chosen macrocycle, the counter-ion, and the solvent have a direct impact on the chemical species formed in solution.
keywords
CROWN THIOETHER CHEMISTRY; X-RAY-STRUCTURE; EFFECTIVE CORE POTENTIALS; ORGANOMETALLIC MACROCYCLE CHEMISTRY; THIOPHENOPHANE METAL-COMPLEXES; S BOND-CLEAVAGE; ELECTROSPRAY MASS-SPECTROMETRY; REDOX NON-INNOCENCE; CRYSTAL-STRUCTURE; STRUCTURAL-CHARACTERIZATION
subject category
Chemistry
authors
Madureira, J; Santos, TM
our authors
Teresa Margarida dos Santos
Retired Professoracknowledgements
Dr Paula Ferreira and Prof. Graca Santana-Marques (University of Aveiro) are thanked for running solid-state 13C NMR and ESI-MS analysis, respectively. J.M. thanks FCT (Portugal) for a post-doc grant (SFRH/BPD/41138/2007) and the Center for High Performance Computing (VCU) for access to bach.vcu.edu cluster.