TY - JOUR
T1 - Tuning of redox properties for the design of ruthenium anticancer drugs: Part 2. Syntheses, crystal structures, and electrochemistry of potentially antitumor [RuIII/IICl6-n(azole)n]z (n = 3, 4, 6) complexes
AU - Reisner, Erwin
AU - Arion, Vladimir B.
AU - Eichinger, Anna
AU - Kandler, Norbert
AU - Giester, Gerald
AU - Pombeiro, Armando J L
AU - Keppler, Bernhard K.
N1 - CAN 143:398250 78-7 Inorganic Chemicals and Reactions Institute of Inorganic Chemistry-Bioinorganic Environmental and Radiochemistry,University of Vienna,Vienna,Austria. Journal 332405-33-1 Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or reagent) (electrochem. properties and solvolysis kinetics upon redn. of ruthenium indazole complex); 180402-64-6; 372492-01-8; 850007-61-3; 866530-82-7; 866530-83-8; 866530-84-9; 866530-86-1; 866530-88-3; 866530-90-7; 866530-92-9; 866530-93-0; 866530-94-1; 866530-95-2; 866604-29-7 Role: CPS (Chemical process), FMU (Formation, unclassified), PEP (Physical, engineering or chemical process), PRP (Properties), FORM (Formation, nonpreparative), PROC (Process) (electrochem. properties of ruthenium azole complexes); 184686-63-3 (Hexakis(imidazole)ruthenium(2+) bis(trifluoromethanesulfonate) Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), PROC (Process) (electrochem. properties of ruthenium imidazole complex); 332405-35-3; 849938-92-7 Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), PROC (Process) (electrochem. properties of ruthenium indazole complex); 866530-67-8P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and crystal structure of ruthenium benzimidazole complex); 866530-71-4P; 866530-76-9P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and crystal structure of ruthenium triazole complex); 124875-12-3P; 866530-66-7P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn. and electrochem. properties of ruthenium benzimidazole complex); 866530-68-9P; 866530-73-6P; 866530-75-8P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn. and electrochem. properties of ruthenium triazole complex); 51-17-2 (Benzimidazole); 288-13-1 (Pyrazole); 288-32-4 (Imidazole); 288-88-0 (1H-1,2,4-Triazole); 4316-42-1 (1-Butylimidazole); 6086-21-1 (1-Methyl-1,2,4-triazole); 7554-65-6 (4-Methylpyrazole); 30066-40-1 (trans-Tetrakis(acetonitrile)dichlororuthenium); 32663-14-2; 74077-58-0; 101461-85-2 (Hexakis(dimethylformamide)ruthenium(3+) tris(trifluoromethanesulfonate); 124951-57-1; 313673-91-5; 385820-41-7 (Hexakis(acetonitrile)ruthenium(2+) tetrachlorozincate(2-); 866530-80-5; 866530-81-6 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of ruthenium azole complexes); 866530-78-1P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of ruthenium triazole complex); 866530-65-6P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn., crystal structure and electrochem. properties of ruthenium imidazole complex); 866530-72-5P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (prepn., crystal structure and electrochem. properties of ruthenium pyrazole complex); 866530-60-1P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn., crystal structure, electrochem. properties and solvolysis kinetics upon redn. of ruthenium imidazole complex); 866530-63-4P; 866604-28-6P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn., crystal structure, electrochem. properties and solvolysis kinetics upon redn. of ruthenium pyrazole complex); 866530-62-3P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn., crystal structure, electrochem. properties and solvolysis kinetics upon redn. of ruthenium triazole complex); 866530-64-5P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn., crystal structure, electrochem. properties, reaction with addnl. triazole and solvolysis kinetics upon redn. of ruthenium triazole complex); 866530-61-2P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (prepn., electrochem. properties and solvolysis kinetics upon redn. of ruthenium benzimidazole complexes)
PY - 2005/9/19
Y1 - 2005/9/19
N2 - A series of mixed chloro-azole ruthenium complexes with potential antitumor activity, viz., mer-[RuIIICl3(azole)3] (B), trans-[RuIIICl2(azole)4]Cl (C), trans-[Ru IICl2(azole)4] (D), and [RuII(azole) 6](SO3CF3)2 (E), where azole = 1-butylimidazole (1), imidazole (2), benzimidazole (3), 1-methyl-1,2,4-triazole (4), 4-methylpyrazole (5), 1,2,4-triazole (6), pyrazole (7), and indazole (8), have been prepared as a further development of anticancer drugs with the general formula [RuCl4(azole)2]- (A). These compounds were characterized by elemental analysis, IR spectroscopy, electronic spectra, electrospray mass spectrometry, and X-ray crystallography. The electrochemical behavior has been studied in detail in DMF, DMSO, and aqueous media using cyclic voltammetry, square wave voltammetry, and controlled potential electrolysis. Compounds B and a number of C complexes exhibit one RuIII/Ru II reduction, followed, at a sufficiently long time scale, by metal dechlorination on solvolysis. The redox potential values in organic media agree with those predicted by Lever's parametrization method, and the yet unknown EL parameters were estimated for 1 (EL = 0.06 V), 3 (EL = 0.10 V), 4 (EL = 0.17 V), and 5 (EL = 0.18 V). The EL values for the azole ligands 1-8 correlate linearly with their basicity (pKa value of the corresponding azolium acid H2L+). In addition, a logarithmic dependence between the homogeneous rate constants for the reductively induced stepwise replacement of chloro ligands by solvent molecules and the RuIII/RuII redox potentials was observed. Lower E1/2 values (higher net electron donor character of the ligands) result in enhanced kinetic rate constants of solvolysis upon reduction. The effect of the net charge on the Ru III/RuII redox potentials in water is tentatively explained by the application of the Born equation. In addition, the pH-dependent electrochemical behavior of trans-[RuCl2(1,2,4-triazole) 4]Cl is discussed. © 2005 American Chemical Society.
AB - A series of mixed chloro-azole ruthenium complexes with potential antitumor activity, viz., mer-[RuIIICl3(azole)3] (B), trans-[RuIIICl2(azole)4]Cl (C), trans-[Ru IICl2(azole)4] (D), and [RuII(azole) 6](SO3CF3)2 (E), where azole = 1-butylimidazole (1), imidazole (2), benzimidazole (3), 1-methyl-1,2,4-triazole (4), 4-methylpyrazole (5), 1,2,4-triazole (6), pyrazole (7), and indazole (8), have been prepared as a further development of anticancer drugs with the general formula [RuCl4(azole)2]- (A). These compounds were characterized by elemental analysis, IR spectroscopy, electronic spectra, electrospray mass spectrometry, and X-ray crystallography. The electrochemical behavior has been studied in detail in DMF, DMSO, and aqueous media using cyclic voltammetry, square wave voltammetry, and controlled potential electrolysis. Compounds B and a number of C complexes exhibit one RuIII/Ru II reduction, followed, at a sufficiently long time scale, by metal dechlorination on solvolysis. The redox potential values in organic media agree with those predicted by Lever's parametrization method, and the yet unknown EL parameters were estimated for 1 (EL = 0.06 V), 3 (EL = 0.10 V), 4 (EL = 0.17 V), and 5 (EL = 0.18 V). The EL values for the azole ligands 1-8 correlate linearly with their basicity (pKa value of the corresponding azolium acid H2L+). In addition, a logarithmic dependence between the homogeneous rate constants for the reductively induced stepwise replacement of chloro ligands by solvent molecules and the RuIII/RuII redox potentials was observed. Lower E1/2 values (higher net electron donor character of the ligands) result in enhanced kinetic rate constants of solvolysis upon reduction. The effect of the net charge on the Ru III/RuII redox potentials in water is tentatively explained by the application of the Born equation. In addition, the pH-dependent electrochemical behavior of trans-[RuCl2(1,2,4-triazole) 4]Cl is discussed. © 2005 American Chemical Society.
KW - Oxidation
KW - Redox potential
KW - Reduction (electrochem. properties of ruthenium azole chloro complexes)
KW - Solvolysis kinetics (kinetics of chloride ligand substitution with solvent mols. upon electrochem. redn. of ruthenium azole chloro complexes)
KW - Heterocyclic compounds Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), PROC (Process), RACT (Reactant or reagent) (nitrogen, five-membered,
KW - prepn., crystal structure, electrochem. properties and solvolysis kinetics of ruthenium azole chloro complexes)
KW - Crystal structure
KW - Molecular structure (of ruthenium azole chloro complexes)
KW - ruthenium azole prepn structure electrochem solvolysis kinetic
KW - crystal structure ruthenium chloro azole complex
U2 - 10.1021/ic0503737
DO - 10.1021/ic0503737
M3 - Article
SN - 0020-1669
VL - 44
SP - 6704
EP - 6716
JO - Inorganic Chemistry: including bioinorganic chemistry
JF - Inorganic Chemistry: including bioinorganic chemistry
IS - 19
ER -
