Solution and solid-state spectroscopic characterization of chloro dimethylsulfoxide polythioether ruthenium(II) complexes, complemented with DFT calculations in the gas phase

authors	Madureira, J; Santos, TM
nationality	International
journal	JOURNAL OF COORDINATION CHEMISTRY
author keywords	Ruthenium; Crown thioethers; Counter-ion; Solvolysis; Molecular modeling
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
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.
publisher	TAYLOR & FRANCIS LTD
issn	0095-8972
year published	2013
volume	66
issue	5
beginning page	881
ending page	903
digital object identifier (doi)	10.1080/00958972.2013.770846
web of science category	Chemistry, Inorganic & Nuclear
subject category	Chemistry
unique article identifier	WOS:000320914400014