Preparation of organometallic ruthenium-arene-diaminotriazine complexes as binding agents to DNA.
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·BF(4), 1·TsO; arene=benzene: 2·BF(4), 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·BF(4) and 3·H(2)O were determined by X-ray diffraction. Complex 1·BF(4) 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·BF(4) was the only species present in solution, even at low ionic strength. However, in alkaline medium (KOH), complex 1·BF(4) underwent basic hydrolysis to afford a Ru-OH complex (5). Fluorimetric studies revealed that the interaction of complex 1·BF(4) 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·BF(4) 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.
Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Plaza Misael Bañuelos s.n., 09001, Burgos, Spain.
Natalia
N
Busto
Jesús
J
Valladolid
Cristina
C
Aliende
Félix A
FA
Jalón
Blanca R
BR
Manzano
Ana M
AM
Rodríguez
Jorge F
JF
Gaspar
Celia
C
Martins
Tarita
T
Biver
Gustavo
G
Espino
José María
JM
Leal
Begoña
B
García
D000818:Animals; D016466:CHO Cells; D056831:Coordination Complexes / Q000737:chemistry* / Q000633:toxicity; D006224:Cricetinae; D003412:Cricetulus; D018360:Crystallography, X-Ray; D000081007:Cymenes; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D008968:Molecular Conformation; D039821:Monoterpenes / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D014227:Triazines / Q000737:chemistry*
D056831:Coordination Complexes; D000081007:Cymenes; D039821:Monoterpenes; D014227:Triazines; C007210:4-cymene; D012428:Ruthenium; D004247:DNA