TY - JOUR
T1 - Synthesis, characterization, and linkage isomerism in mononuclear ruthenium complexes containing the new pyrazolate-based ligand hpbl
AU - Francàs, Laia
AU - González-Gil, Rosa M.
AU - Poater, Albert
AU - Fontrodona, Xavier
AU - García-Antón, Jordi
AU - Sala, Xavier
AU - Escriche, Lluís
AU - Llobet, Antoni
PY - 2014/8/4
Y1 - 2014/8/4
N2 - A new tetradentate dinucleating ligand [1,1′-(4-methyl-1H-pyrazole-3, 5-diyl)bis(1-(pyridin-2-yl)ethanol)] (Hpbl) containing an O/N mixed donor set of atoms has been synthesized and characterized by analytical and spectroscopic techniques. The Ru-Cl and Ru-aqua complexes containing this ligand of general formula [RuIIX(Hpbl)(trpy)]y+ (trpy = 2,2′:6′, 2″-terpyridine; X = Cl, y = 1; X = H2O, y = 2) have been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The Ru-aqua complex 2 undergoes N → O linkage isomerization as observed electrochemically, and the related thermodynamic and kinetic parameters are extracted from cyclic voltammetry experiments together with DIGISIM, a CV simulation package. Under basic conditions an additional isomer is observed where the pyrazolyl group in the Hpbl ligand is replaced by the geminal pyridyl group. Further structural and electronic characterization of all the isomers has been carried out by means of DFT calculations. © 2014 American Chemical Society.
AB - A new tetradentate dinucleating ligand [1,1′-(4-methyl-1H-pyrazole-3, 5-diyl)bis(1-(pyridin-2-yl)ethanol)] (Hpbl) containing an O/N mixed donor set of atoms has been synthesized and characterized by analytical and spectroscopic techniques. The Ru-Cl and Ru-aqua complexes containing this ligand of general formula [RuIIX(Hpbl)(trpy)]y+ (trpy = 2,2′:6′, 2″-terpyridine; X = Cl, y = 1; X = H2O, y = 2) have been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The Ru-aqua complex 2 undergoes N → O linkage isomerization as observed electrochemically, and the related thermodynamic and kinetic parameters are extracted from cyclic voltammetry experiments together with DIGISIM, a CV simulation package. Under basic conditions an additional isomer is observed where the pyrazolyl group in the Hpbl ligand is replaced by the geminal pyridyl group. Further structural and electronic characterization of all the isomers has been carried out by means of DFT calculations. © 2014 American Chemical Society.
U2 - 10.1021/ic5009076
DO - 10.1021/ic5009076
M3 - Article
SN - 0020-1669
VL - 53
SP - 8025
EP - 8035
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -