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ABSTRACT: The new water soluble complexes [RuClCp(HPTA)2]Cl2·2H2O (), [RuCp(DMSO-κS)(PTA)2]Cl (), [RuCp(DMSO-κS)(PTA)2](OSO2CF3) () and [RuCp(DMSO-κS)(HPTA)2]Cl3·2H2O () have been synthesized and fully characterized by NMR, IR and elemental analysis. The structures of complexes and were also characterized by single crystal X-ray determination. The catalytic activity of the complexes and [RuClCp(PTA)2] () for the isomerisation in water of 1-octen- to 1-penten-3-ol was assessed and discussed.
Dalton Transactions 03/2013; · 3.84 Impact Factor
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ABSTRACT: The biological evaluation of new Ru(II) complexes carrying dmoPTA (dmoPTA=3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) ligands is reported. The results on the biological activity revealed that the organometallic complexes are active against all cell lines with GI(50) values in the range 1.1-2.6 μM. When compared to the standard anticancer drug cisplatin, the bimetallic Ru(II) complexes showed a greater activity profile. The cell cycle analysis revealed that the new compounds induced arrest in G(1) phase. Contrary to cisplatin, these Ru(II) complexes do not interact with DNA. This result suggests that DNA might not be the key pharmacological target.
Bioorganic & medicinal chemistry letters 06/2011; 21(15):4568-71. · 2.65 Impact Factor
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ABSTRACT: The synthesis of novel heterobimetallic derivatives of general formula [RuClCp(PPh(3))-μ-dmoPTA-1κP:2κ(2)N,N'-M(acac-κ(2)O,O')(2)] (M = Ni (3), Zn (4); dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) is described. The preparations of the ruthenium-cobalt analogue (M = Co (2)) and the starting compound [RuClCp(HdmoPTA-κP)(PPh(3))](CF(3)SO(3)) have been revised and their yield improved. Similar to 2, the solid state structures of 3 and 4 show that the dmoPTA-P and the dmoPTA-N(CH(3)) atoms are involved in the coordination to the {RuCpCl(PPh(3))} and {M(acac)(2)} moieties, respectively. The size of the diffusing units is almost the same for the three binuclear complexes, indicating that they exhibit similar solution structures. The diamagnetic ruthenium-zinc derivative was fully characterized in solution at 193 K by NMR as two diastereomeric pairs of enantiomers (R-Ru, Δ-Zn; R-Ru, Λ-Zn; S-Ru, Δ-Zn; S-Ru, Λ-Zn). Finally, the electrochemical properties of the complexes have been investigated by cyclic voltammetry.
Dalton Transactions 02/2011; 40(13):3237-44. · 3.84 Impact Factor
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ABSTRACT: The new water-soluble ruthenium(II) mononuclear complexes [RuCp(X)(PTA)(L)] (X = 8-thio-theophyllinate (TTH(-)), L = PTA (1), L = PPh(3) (7)); (X = 8-methylthio-theophyllinate (8-MTT(-)), L = PTA (2), L = PPh(3) (8)), (X = 8-benzylthio-theophyllinate (8-BzTT(-)), L = PTA (3), L = PPh(3) (9)) and binuclear complexes [{RuCp(PTA)(L)}(2)-μ-(Y-κN7,N'7)] (Y = bis(S-8-thiotheophyllinate)methane (MBTT(2-)), L = PTA (4), L = PPh(3) (10)), (Y = 1,2-bis(S-8-thiotheophyllinate)ethane (EBTT(2-)), L = PTA (5), L = PPh(3) (11)), (Y = 1,3-bis(S-8-thiotheophyllinate)propane (PBTT(2-)); L = PTA (6), L = PPh(3) (12)) have been synthesized and characterized by NMR, IR spectroscopy and elemental analysis. The single crystal X-ray structure of [RuCp(8-MTT-κS)(PTA)(2)] (2) was also obtained. The antiproliferative activity of the complexes on cisplatin-sensitive T2 and cisplatin-resistant SKOV3 cell lines has been evaluated.
Inorganic Chemistry 02/2011; 50(3):873-82. · 4.60 Impact Factor
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ABSTRACT: On irradiating the complex cis-[RuCl(2)(mPTA)(4)](CF(3)SO(3))(4) (2) with near UV light at room temperature, (OC-6-13)-[RuCl(2)(mPTA)(3)(H(2)O)](CF(3)SO(3))(3) (3) was obtained. Complex 3 is the product of the substitution in 2 of one mPTA by a H(2)O molecule and the rearrangement from cis to trans of the two chlorides. The selective photo-reaction of 2 is produced with radiation of 300 < λ < 400 nm or with λ = 367 nm in 50 min (Φ(367 nm) (D(2)O) = 0.18 ± 0.01). The reaction is not reversible with visible light. The transformation of 2 into 3 is not dependent on the pH but only on the radiation used. Reaction of 3 with NaCl leads to (OC-6-21)-[RuCl(3)(mPTA)(3)](CF(3)SO(3))(2) (4) which could be directly obtained by irradiation of 2 with λ = 367 nm in water and 5 eq. of NaCl (Φ(367 nm) (D(2)O) = 0.17 ± 0.01). Complex 4 turns slowly to 2 in water with 1 eq. of mPTA under light of λ > 416 nm. Complete conversion of 4 into 2 was achieved after more than one day. All complexes were characterized by elemental analysis, IR and NMR spectroscopy, and 2, 3 and 4 by single crystal X-ray determination. An easy synthesis for the ligand mPTA(CF(3)SO(3)) is also reported.
Dalton Transactions 01/2011; 40(4):828-36. · 3.84 Impact Factor
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ABSTRACT: Ruthenium(II) complexes are of great interest as a new class of cancerostatics with advantages over classical platinum compounds including lower toxicity. The stability of the [RuClCp(mPTA)2](OSO2CF3)2 complex (I) (Cp cyclopentadienyl, mPTA N-methyl 1,3,5-triaza-7-phosphaadamantane) in aqueous solution was studied using spectrophotometry, matrix-assisted laser desorption/ionization (MALDI) and laser desorption/ionization (LDI) time-of-flight (TOF) mass spectrometry (MS). Spectrophotometry proves that at least three different reactions take place in water. Dissolution of I leads to fast coordination of water molecules to the Ru(II) cation and then slow hydrolysis and ligand exchange of chloride and mPTA with water, hydroxide or with trifluoromethane sulfonate itself. Via MALDI and LDI of the hydrolyzed solutions the formation of singly positively charged ions of general formula RuCl(p)(Cp)(q)(mPTA)(r)(H2O)(s)(OH)(t) (p = 0-1, q = 0-1, r = 0-2, s = 0-5, t = 0-2) and of some fragment ions was shown. The stoichiometry was determined by analyzing the isotopic envelopes and computer modelling. The [RuClCp(mPTA)2](OSO2CF3)2 complex can be stabilized in dilute hydrochloric acid or in neutral 0.15 M isotonic sodium chloride solution.
Rapid Communications in Mass Spectrometry 11/2009; 23(23):3831-6. · 2.79 Impact Factor
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ABSTRACT: Eight new complexes containing the versatile multidentate ligand 5-pyrimidyl-tetrazolate (pmtz), namely [Cu(mu(3)-pmtz)](n) (1), [Pd(2)(mu-pmtz)(2)Cl(2)] (2), [Ni(pmtz)(en)(2)]Cl x 2 H(2)O (3), [Cu(tren)(pmtz)(ClO(4))] (4), [Co(2)(tren)(2)(mu-pmtz)(mu-O(2))](ClO(4))(3) x 3 H(2)O (5), [Fe(2)(pmtz)(4)(H(2)O)(2)(mu-O)] x 5 H(2)O (6), [(UO(2))(4)(mu-pmtz)(2)(mu-OH)(2)(mu(3)-O)(2)(H(2)O)(4)] x 6 H(2)O (7) and [Dy(2)(pmtz)(4)(mu-pmtz)(H(2)O)(6)](pmtz) x 6 H(2)O (8), have been prepared by either conventional solution or hydrothermal techniques and characterised by single-crystal X-ray diffraction. Those compounds prepared under hydrothermal conditions ((1), (2), (7) and (8)) exhibit chelating/bridging coordination modes that connect two or three metal ions generating polynuclear species. Thus, compound is a 2D polymer where the ligand exhibits a new chelating/bridging kappa(2)N(1),N(7):kappaN(2):kappaN(3) coordination mode, whereas complexes (2) and (7) are dinuclear and tetranuclear species, respectively, in which the ligand displays a kappa(2)N(1),N(7):kappaN(2) coordination mode. The increase of the metal size favours the adoption of the kappa(2)N(1),N(7):kappa(2)N(4),N(11) bis(chelating)bridging mode. This is the case of compound (8) that contains bulky Dy(III) metal ions. Despite the large size of the UO(2+) metal ion, the pmtz ligand in (7) does not adopt the expected bis(chelating)bridging mode because the uranyl cation hydrolyzes to the highly stable bis(mu(3)-oxo) tetranuclear unit. Conventional mild solution conditions lead to complexes containing monodentate or chelating coordination modes. Thus, compounds (3) and (6) are mononuclear and mu-oxo dinuclear species, respectively, which contain kappa(2)N(1),N(7) chelating pmtz ligands. Compound (4) is mononuclear with the ligand acting in a new monodentate form through the N(1) atom of the tetrazolato ring, whereas (5) is a dinuclear complex where pmtz adopts a new exo-bidentate N(2),N(3) bridging coordination mode. Variable-temperature magnetic measurements of (6) indicate that the oxo-bridge mediates a very strong antiferromagnetic interaction between the iron(III) ions with a J = -222.7 cm(-1). Luminescence measurements show that the pmtz ligands act as "antenna" for energy absorption and transfer to the uranyl emissive state.
Dalton Transactions 11/2009; · 3.84 Impact Factor
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ABSTRACT: The interaction of the PTA (PTA = 1,3,5-triaza-7-phosphaadamantane) ruthenium complex trans-[RuCl(2)(PTA)(4)] (trans-1) with visible light in chloroform and in water has been studied at room temperature. The complex trans-1 isomerizes to the cis isomer in CHCl(3) with radiation of lambda > 416 nm (Phi(434 nm) (CHCl(3)) = 0.13 +/- 0.01). The isomerization reaction is reversible as cis-1 is transformed into trans-1 with lambda = 367 nm (Phi(367 nm) (CHCl(3)) = 0.25 +/- 0.02). Irradiation at lambda > 416 nm of a solution of trans-1 in water leads to the cis-isomer complex and to the aqua complex (OC-6-32)-[RuCl(H(2)O)(PTA)(4)]Cl (2Cl) by a photoisomerization and photoaquation reaction (Phi(434 nm) (D(2)O) = 0.27 +/- 0.02). The mole ratio of cis-1 to 2Cl is not dependent on the pH but on the concentration of the products in solution. Isomerization in water is not reversible even if only cis-1 is present in solution. Synthesis and characterization of (OC-6-32)-[RuCl(H(2)O)(PTA)(4)](CF(3)SO(3)) (2CF(3)SO(3)) are also presented.
Inorganic Chemistry 04/2009; 48(8):3692-8. · 4.60 Impact Factor
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ABSTRACT: The reactions between oligoethylene glycol diglycidyl ethers 2a-c with both 7-hydroxy-4-methyl-2H-chromen-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 1H NMR, 13C{1H} NMR, 2D-1H-13C HMBC, 2D-1H 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.
Journal of Heterocyclic Chemistry 03/2009; 45(6):1835 - 1842. · 1.22 Impact Factor
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Angewandte Chemie International Edition 11/2008; 47(45):8665-9. · 13.45 Impact Factor
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ABSTRACT: The dinuclear complex [RuClCp(PPh3)-mu-dmoPTA-1kappa P:2kappa(2)N, N'-Co(acac-kappa(2)O, O') 2].H 2O (2; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) has been synthesized by reaction of [RuClCp(HdmoPTA)(PPh3)](OSO2CF3) (1) with Co(acac)2 in methanol (HdmoPTA = 3,7-H-3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane). Elemental analysis, IR, NMR, and single-crystal X-ray structure determination have characterized the new complex. This complex is active for the catalytic isomerization of but-1-en-3-ol in acetone better than 1.
Inorganic Chemistry 05/2008; 47(7):2246-8. · 4.60 Impact Factor
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ABSTRACT: Ring opening of amino epoxides derived from naturally occurring amino acids with lithium diphenylphosphido borane is reported as an efficient approach to a new family of enantiomerically enriched multifunctional phosphines.
The Journal of Organic Chemistry 10/2007; 72(20):7787-9. · 4.45 Impact Factor
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ABSTRACT: 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.
Inorganic Chemistry 08/2007; 46(15):6120-8. · 4.60 Impact Factor
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ABSTRACT: We report here the synthesis of newly coumarinic derivatives by using 4-hydroxy coumarine as starting
material. These newly compounds were screened in vitro for their antimicrobial and antifungal activities.
The structures of the synthesized compounds were proved by IR, 1
HNMR,
13
CNMR and mass-spectral.
06/2007: pages 283-301;
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Berichte der deutschen chemischen Gesellschaft 05/2007; 2007(18):2803 - 2812. · 2.94 Impact Factor
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03/2007: pages 169 - 453; , ISBN: 9780470166512
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ABSTRACT: Halogen complexes of ruthenium cyclopentadienyl [CpRu(PTA)(2)X]; [CpRu(PTA)(PPh3)X]; [CpRu(PPh3)(2)Cl], and [CpRu(mPTA)(PPh3)X](+) (Cp = C5H5; PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA(+) = [1-methyl-1,3,5-triaza-7-phosphaadamantane](+) ; X = Cl-, I-) were investigated by electrospray mass spectrometry (ESI-MS), in flow-cell cyclic voltammetry, by microelectrodes, and by combined online electrochemistry and electrospray mass spectrometry (EC/ESI-MS) in dimethyl formamide solution. Coordination changes and the structures of the initial compounds and the products of the electrooxidation of the Ru(II) complexes were traced by in situ EC/MSn experiments which revealed their fragmentation pathways. ESI-MS collision-induced dissociation fragmentations of the initial reactants and the oxidation products were explained by soft acid-hard base considerations taking into account the different nature of Ru(II)-Ru(IV) centers. The electrochemical studies show that it is possible to tune the formal potentials for the oxidation of [CpRuL2X] complexes by over 300 mV by proper selection of the ligands. The increase of the redox potential by the different ligands follows the order PTA < PPh3 < mPTA(+). We demonstrate a similarity between the propensity of the ligand to fragment out in the gas phase and its relationship to the formal potential of the complex. (c) 2006 The Electrochemical Society.
Journal of The Electrochemical Society 01/2007; 154(1):F7-F15. · 2.59 Impact Factor
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ABSTRACT: 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.
Inorganic Chemistry 03/2006; 45(3):1289-98. · 4.60 Impact Factor
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ABSTRACT: The chemistry of phosphorus is nowadays rivaling that of carbon in terms of complexity and diversity. This tutorial review highlights the state-of-the-art in the field of metal-mediated activation and functionalization of white phosphorus. Particular attention is given to an illustration of the coordination abilities of the intact molecule as well as the disaggregating and reaggregating metal-mediated processes resulting in different polyphosphorus ligands from P(1) to P(12). The metal-promoted P-C and P-H bond forming processes are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds is a concrete possibility for chemical companies. This tutorial review deals with the activation and functionalization of white phosphorus in the coordination sphere of transition metal complexes. Particular attention is given to the coordination abilities of the intact molecule as well as to the disaggregating and reaggregating metal-mediated processes yielding various polyphosphorus ligands from P(1) to P(12). The metal-promoted processes for P-C and P-H bond formation are also reviewed showing that an ecoefficient catalytic protocol for transforming P(4) into high value organophosphorus compounds offers good opportunities for chemical companies.
Chemical Society Reviews 01/2006; 34(12):1038-47. · 28.76 Impact Factor
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Angewandte Chemie International Edition 05/2005; 44(17):2568-72. · 13.45 Impact Factor
