The new water-soluble ruthenium(II) chiral complexes [RuCpX(L)(L')](n+) (X = Cl, I. L = PPh3; L' = PTA, mPTA; L = L' = PTA, mPTA) (PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) have been synthesized and characterized by NMR and IR spectroscopy and elemental analysis. The salt mPTA(OSO2CF3) was also prepared and fully characterized by spectroscopic techniques. X-ray crystal structures of [RuClCp(PPh3)(PTA)] (2), [RuCpI(PPh3)(PTA)] (3), and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9) have been determined. The binding properties toward DNA of the new hydrosoluble complexes have been studied using the mobility shift assay. The ruthenium chloride complexes interact with DNA depending on the hydrosoluble phosphine bonded to the metal, while the corresponding compounds with iodide, [RuCpI(PTA)2] (1), [RuCpI(PPh3)(PTA)] (3), [RuCpI(mPTA)2](OSO2CF3)2 (6), and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9), do not bind to DNA.
Reaction of the water-soluble ruthenium complex [{RuCl 2 (TPPMS) 2 }Na 2 ] 2 ‚4H 2 O with phenylacetylene and diphenylpropargyl alcohol in THF at room temperature gave the water-soluble unsaturated carbenes [{RuCl 2 {CdC(H)Ph}(TPPMS) 2 }]Na 2 and [{RuCl(µ-Cl)-(CdCdCPh 2 )(TPPMS) 2 } 2 ]Na 4 , respectively. The ability of these complexes, which represents the first example of water-soluble vinylidenes and allenylidenes, to catalyze the ring-opening metathesis of cyclic olefins with methyl acrylate as chain transfer reagents is briefly discussed.
The new water-soluble ligand dmPTA(OSO(2)CF(3))(2) (1) (dmPTA = N,N'-dimethyl-1,3,5-triaza-7-phosphaadamantane) has been synthesized by reaction of PTA with MeOSO(2)CF(3) in acetone (PTA = 1,3,5-triaza-7-phosphatricycle[3.3.1.1(3,7)]decane). The reaction of 1 with KOH gave rise to the new water-soluble ligand dmoPTA (3) (dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) by elimination of the -CH(2)- group located between both NCH(3) units. Compound dmPTA(BF(4))(2) (2) and complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (4) have also been synthesized, while compounds HdmoPTA(BF(4)) (3a) and [RuClCp(dmPTA)(PPh(3))](OSO(2)CF(3)) (5) were characterized but not isolated. The new ligands and the complex have been fully characterized by NMR, IR, elemental analysis, and X-ray crystal structure determination (ligand 1 and complex 4). The synthetic processes for 3 and 4 were studied.
The water-soluble ruthenium allenylidene complex [{RuCl(µ-Cl)(C=C=CPh 2 )(TPPMS) 2 } 2 ]Na 4 catalyses the selective transformation of substituted linear and cyclic vinyl ethers with MeOH, under mild non acidic conditions, to give acetals, while aldehydes and ketones are obtained in a CHCl 3 /H 2 O
O OH O N N R a: R=H b: R=Ph O OH O O OH O O NMe 2 NH 2 NHR Toluene 6a-bThe reactions between oligoethylene glycol diglycidyl ethers 2a-c with both 7-hydroxy-4-methyl-2Hchromen-2-one and 4-hydroxy-2H-chromen-2-one lead to new hydroxy ethers 3 and 4 containing coumarin moieties in good yield. The synthesis of 3-(3-(dimethylamino)acryloyl)-4-hydroxy-2H-chromen-2-one 5 and new heterocyclic compounds 4-hydroxy-3-(1H-pyrazol-3-yl)-2H-chromen-2-one 6a, 4-hydroxy-3-(1-phenylpyrazol-3-yl)-2H-chromen-2-one 6b and 4-hydroxy-3-(isoxazol-3-yl)-2H-chromen-2-one 6c is also described. All compounds were characterized by 1 H NMR, 13 C{ 1 H} NMR, 2D-1 H-13 C HMBC, 2D-1 H NOESY NMR, IR, and MS spectroscopy. Additionally, the antibacterial activity of the new products containing coumarin moiety was evaluated. This activity is clearly dependent on the chemical structure of compounds.
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