The new complex [(η 6 -p-cym)RuCl(κ 2 -N,N-dmbpy)](BF 4 ) (pcym = p-cymene; dmbpy = 4,4′-dimethyl-2,2′-bipyridine) is water-soluble and active in the catalytic transfer hydrogenation (TH) of different ketones (cyclohexanone, 2-cyclohexenone, and 3-pentanone) to the corresponding alcohols using aqueous HCOONa/HCOOH as the hydrogen source at pH 4.4. A higher activity was found for the TH of the imine N-benzylideneaniline under the same conditions. Excellent results have been obtained for catalyst recycling. Aqua, formato, and hydrido species were detected by 1 H NMR experiments in D 2 O. Importantly, when the catalytic reaction was carried out in D 2 O, selective deuteration at the C α of the alcohols was observed due to a rapid Ru−H/D + exchange, which was also deduced theoretically. This process involves a reversal of polarity of the D + ion, which is transformed into a Ru−D function ("umpolung"). Negligible deuterium labeling was observed for the imine, possibly due to the high activity in the TH process and also to the decrease in the hydrido complex concentration due to the stability of a hydrido-imine intermediate. Both facts should ensure that the TH reaction will compete favorably with the Ru−H/D + exchange. The basic nature of the imine hydrogenation product can also hinder the stated Ru−H/D + exchange. On the basis of DFT calculations, all these hypotheses are discussed. In addition, calculations at this level also support the participation of the stated aqua, formato, and hydrido intermediates in the catalytic reaction and provide a detailed microscopic description of the full catalytic cycle. In the case of the imine TH process, the formation of the hydrido complex (decarboxylation step) is clearly the limiting step of the cycle. On the contrary, in the hydrogenation of cyclohexanone, both decarboxylation and reduction steps exhibit similar barriers, and due to the limitations of the solvent model employed, a definitive conclusion on the rate-determining step cannot be inferred.
The preparation of three series of arene Ru(II) half-sandwich compounds with the functional ligand 4,4′-dimethoxy-2,2′-bipyridine (dmobpy) is described. The new cationic derivatives have the general formula [(η6-arene)RuCl(κ2-N,N-dmobpy)]X (arene = benzene, X = Cl– ([1]Cl), BF4 – ([1][BF 4 ]), TsO– ([1]TsO), PF6 – ([1][PF 6 ]); arene = p-cymene (p-cym), X = Cl– ([2]Cl), BF4 – ([2][BF 4 ]), TsO– ([2]TsO), PF6 – ([2][PF 6 ]); arene = 2-phenoxy-1-ethanol (phoxet), X = Cl– ([3]Cl), BF4 – ([3][BF 4 ]), TsO– ([3]TsO), PF6 – ([3][PF 6 ])). The structures of [1]Cl, [1]TsO, [2]TsO, [2][BF 4 ], and [2][PF 6 ] were determined by X-ray crystallography. All of the complexes except the PF6 – salts were water-soluble, and they behaved as active catalysts in two different processes: the transfer hydrogenation of water-soluble and -insoluble ketones to the corresponding alcohols, using HCOONa as the hydrogen source at pH 4, and the oxidation of rac-1-phenylethanol to acetophenone with tBuOOH at pH 7, both in aqueous solution. For the transfer hydrogenation with p-cymene complexes the aqua, formato, and hydride species were detected by means of 1H NMR experiments in D2O. It was found that the cationic hydrido complex was [(η6-p-cymene)RuD(dmobpy)]+. The reversible and pH-dependent formation of the hydroxo derivative was also observed. When the catalytic transfer hydrogenation was performed in D2O, the 1-phenylethanol obtained was selectively deuterated at the benzylic carbon. Mechanistic proposals are also included.
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.
The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in neoplastic cell lines.
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