TY - JOUR
T1 - Solvent Effects on the Oxidative Electrochemical Behavior of cis-Bis(isothiocyanato)ruthenium(II)-bis-2,2'-bipyridine-4,4'-dicarboxylic Acid
AU - Cecchet, Francesca
AU - Gioacchini , Anna Maria
AU - Marcaccio, Massimo
AU - Paolucci , Francesco
AU - Roffia , Sergio
AU - Alebbi , Monica
AU - Bignozzi , Carlo Alberto
PY - 2002/4/1
Y1 - 2002/4/1
N2 - The redox properties of cis-[Ru(dcbpyH2)2(NCS)2] ([Ru(dcbpyH2)2(NCS)2]; dcbpyH2 = 2,2‘-bipyridine- 4,4‘-dicarboxylic acid) have been investigated in various solvents by combining electrochemical techniques (cyclic voltammetry (CV) and spectroelectrochemistry), mass spectrometry, digital simulation techniques, and semiempirical quantum chemical calculations. The electrochemical study has shown that while in polar solvents such as acetonitrile and ethanol the complex undergoes, following oxidation, the rapid loss of SCN ligands, forming the corresponding solvato complexes. In the less polar solvent tetrahydrofuran, a reversible oxidative CV behavior is observed at relatively low scan rates. On the basis of the CV and spectroelectrochemical studies and supported by quantum chemical calculations, a complex parallel ECE mechanism is proposed, comprising the loss of the SCN ligands in their pristine (anionic) form, which is initiated by the metal-centered oxidation process.
AB - The redox properties of cis-[Ru(dcbpyH2)2(NCS)2] ([Ru(dcbpyH2)2(NCS)2]; dcbpyH2 = 2,2‘-bipyridine- 4,4‘-dicarboxylic acid) have been investigated in various solvents by combining electrochemical techniques (cyclic voltammetry (CV) and spectroelectrochemistry), mass spectrometry, digital simulation techniques, and semiempirical quantum chemical calculations. The electrochemical study has shown that while in polar solvents such as acetonitrile and ethanol the complex undergoes, following oxidation, the rapid loss of SCN ligands, forming the corresponding solvato complexes. In the less polar solvent tetrahydrofuran, a reversible oxidative CV behavior is observed at relatively low scan rates. On the basis of the CV and spectroelectrochemical studies and supported by quantum chemical calculations, a complex parallel ECE mechanism is proposed, comprising the loss of the SCN ligands in their pristine (anionic) form, which is initiated by the metal-centered oxidation process.
U2 - https://doi.org/10.1021/jp014343a
DO - https://doi.org/10.1021/jp014343a
M3 - Article
SN - 1520-5207
VL - 106
SP - 3926
EP - 3932
JO - The Journal of Physical Chemistry B
JF - The Journal of Physical Chemistry B
IS - 15
ER -