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Preparation of Organometallic Ruthenium–Arene–Diaminotriazine Complexes as Binding Agents to DNA
Author(s) -
Busto Natalia,
Valladolid Jesús,
Aliende Cristina,
Jalón Félix A.,
Manzano Blanca R.,
Rodríguez Ana M.,
Gaspar Jorge F.,
Martins Celia,
Biver Tarita,
Espino Gustavo,
Leal José María,
García Begoña
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100883
Subject(s) - ruthenium , chemistry , cationic polymerization , bifunctional , medicinal chemistry , aquation , triazine , ionic strength , ionic bonding , stereochemistry , organic chemistry , ion , catalysis , physics , quantum mechanics , aqueous solution , kinetics , reaction rate constant
The reactions of two diaminotriazine ligands 2,4‐diamino‐6‐(2‐pyridyl)‐1,3,5‐triazine (2‐pydaT) and 6‐phenyl‐2,4‐diamino‐1,3,5‐triazine (PhdaT) with ruthenium–arene precursors led to a new family of ruthenium(II) compounds that were spectroscopically characterized. Four of the complexes were cationic, with the general formula [( η 6 ‐arene)Ru( κ 2 ‐ N , N ‐2‐pydaT)Cl]X (X=BF 4 , TsO; arene= p ‐cymene: 1.BF4 , 1.TsO arene=benzene: 2.BF4 , 2.TsO ). The neutral cyclometalated complex [( η 6 ‐ p ‐cymene)Ru( κ 2 ‐ C , N ‐PhdaT*)Cl] ( 3 ) was also isolated. The structures of complexes 2.BF4 and 3.H2O were determined by X‐ray diffraction. Complex 1.BF4 underwent a partial reversible‐aquation process in water. UV/Vis and NMR spectroscopic measurements showed that the reaction was hindered by the addition of NaCl and was pH‐controlled in acidic solution. At pH 7.0 (sodium cacodylate) Ru–Cl complex 1.BF4 was the only species present in solution, even at low ionic strength. However, in alkaline medium (KOH), complex 1.BF4 underwent basic hydrolysis to afford a Ru–OH complex ( 5 ). Fluorimetric studies revealed that the interaction of complex 1.BF4 with DNA was not straightforward; instead, its main features were closely linked to ionic strength and to the [DNA]/complex ratio. The bifunctional complex 1.BF4 was capable of interacting concurrently through both its p ‐cymene and 2‐pydaT groups. Cytotoxicity and genotoxicity studies showed that, contrary to the expected behavior, the complex species was biologically inactive; the formation of a Ru–OH complex could be responsible for such behavior.