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.

One of the latest trends in supramolecular chemistry is the quest for reproducible methods to achieve controlled selforganization of discrete units to form homo-and heterometallic coordination networks, aggregates, and polymers.[1] This development is based on the use of appropriate organic, inorganic, and organometallic building blocks that allow the synthesis of 1D linear or twisted chains, 2D squares and polygons, and 3D cubes and polyhedra.[2] Among the organic spacers, nitrogen-based aromatic heterocycles are the most widely used due to their good donor properties and rigidity. These ligands can act as corner units (bipy, phen) [3] and spacers (pyrazines, [4] terpy, [5] porphyrinates, [6] tetraazamacrocycles [7] ). P-donor ligands as spacers have received less attention:[8] P 2 and P 5 ligands have been studied by Scheer and co-workers, [9] whereas the use of multidentate phosphanes has been reviewed recently.[10] To the best of our knowledge, the use of mixed N,P ligands as metal-coordinating spacers has not been reported to date.Very few coordination polymers are water soluble, an example being the poly(ferrocenylsilane)-b-poly(aminomethacrylate) copolymer recently described by Manners and coworkers [11] as part of their ongoing study on metallocenebased polymers, [12] which can be prepared by ring-opening polymerization to afford either macromolecules with pendant ferrocenyl substituents in the polymer side chains [13] or poly(ferrocenylsilane)s. [14] Other examples of ligands that afford coordination polymers with various topologies and applications are ferrocenyl ligands bearing bipyridines [15] or carboxylates.[16]Herein we describe the first known case of a watersoluble, air-stable, heterobimetallic polymeric structure based on two metal-containing moieties ([CpRu] + and [AgCl 2 ] À ) bridged by a cagelike, water-soluble monodentate phosphane, 1,3,5-triaza-7-phosphaadamantane (pta), in an unprecedented N,P coordinating mode.We recently reported the synthesis and characterization of the water-soluble cyclopentadienylruthenium complex [CpRuCl(pta) 2 ] (1), which is stabilized by the phosphaadamantane-like pta ligand, and described its catalytic and biological properties.[17] As part of our studies on new water-soluble organometallic derivatives based on the [CpRu(pta) 2 ] + moiety, [18] we treated 1 with one equivalent of AgOTf (OTf = OSO 2 CF 3 ) in DMSO to remove the chloro ligand. Unexpectedly, no AgCl precipitated from the resulting orange solution, and neither did it contain the expected product [CpRu(OTf)(pta) 2 ] (2), which was obtained by treatment of 1 with TlOTf. [19] Intrigued by this apparently odd result, we repeated the experiment in an NMR tube.31 P{ 1 H} NMR analysis in [D 6 ]DMSO indicated the formation of a 1:1 mixture of the new complex [CpRu(pta) 2 (dmso-kS)]OTf (3; singlet at d = À28.13 ppm) and the bimetallic neutral coordination polymer [{CpRu(pta) 2 (dmso-kS)}{AgCl 2 }] ¥ (4; singlet at d = À23.19 ppm), as shown in Scheme 1.Quantitative formation of 4 could be attained by ...

The water-soluble ruthenium(II) complexes Na 2 [RuCpX-(mTPPMS)

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One of the latest trends in supramolecular chemistry is the quest for reproducible methods to achieve controlled selforganization of discrete units to form homo-and heterometallic coordination networks, aggregates, and polymers.[1] This development is based on the use of appropriate organic, inorganic, and organometallic building blocks that allow the synthesis of 1D linear or twisted chains, 2D squares and polygons, and 3D cubes and polyhedra.[2] Among the organic spacers, nitrogen-based aromatic heterocycles are the most widely used due to their good donor properties and rigidity. These ligands can act as corner units (bipy, phen) [3] and spacers (pyrazines, [4] terpy, [5] porphyrinates, [6] tetraazamacrocycles [7] ). P-donor ligands as spacers have received less attention:[8] P 2 and P 5 ligands have been studied by Scheer and co-workers, [9] whereas the use of multidentate phosphanes has been reviewed recently.[10] To the best of our knowledge, the use of mixed N,P ligands as metal-coordinating spacers has not been reported to date.Very few coordination polymers are water soluble, an example being the poly(ferrocenylsilane)-b-poly(aminomethacrylate) copolymer recently described by Manners and coworkers [11] as part of their ongoing study on metallocenebased polymers, [12] which can be prepared by ring-opening polymerization to afford either macromolecules with pendant ferrocenyl substituents in the polymer side chains [13] or poly(ferrocenylsilane)s. [14] Other examples of ligands that afford coordination polymers with various topologies and applications are ferrocenyl ligands bearing bipyridines [15] or carboxylates.[16]Herein we describe the first known case of a watersoluble, air-stable, heterobimetallic polymeric structure based on two metal-containing moieties ([CpRu] + and [AgCl 2 ] À ) bridged by a cagelike, water-soluble monodentate phosphane, 1,3,5-triaza-7-phosphaadamantane (pta), in an unprecedented N,P coordinating mode.We recently reported the synthesis and characterization of the water-soluble cyclopentadienylruthenium complex [CpRuCl(pta) 2 ] (1), which is stabilized by the phosphaadamantane-like pta ligand, and described its catalytic and biological properties.[17] As part of our studies on new water-soluble organometallic derivatives based on the [CpRu(pta) 2 ] + moiety, [18] we treated 1 with one equivalent of AgOTf (OTf = OSO 2 CF 3 ) in DMSO to remove the chloro ligand. Unexpectedly, no AgCl precipitated from the resulting orange solution, and neither did it contain the expected product [CpRu(OTf)(pta) 2 ] (2), which was obtained by treatment of 1 with TlOTf. [19] Intrigued by this apparently odd result, we repeated the experiment in an NMR tube.31 P{ 1 H} NMR analysis in [D 6 ]DMSO indicated the formation of a 1:1 mixture of the new complex [CpRu(pta) 2 (dmso-kS)]OTf (3; singlet at d = À28.13 ppm) and the bimetallic neutral coordination polymer [{CpRu(pta) 2 (dmso-kS)}{AgCl 2 }] ¥ (4; singlet at d = À23.19 ppm), as shown in Scheme 1.Quantitative formation of 4 could be attained by ...

Halogen complexes of ruthenium cyclopentadienyl ͓CpRu͑PTA͒ 2 X͔; ͓CpRu͑PTA͒͑PPh 3 ͒X͔; ͓CpRu͑PPh 3 ͒ 2 Cl͔, and ͓CpRu͑mPTA͒͑PPh 3 ͒X͔ + ͑Cp = C 5 H 5 ; PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA + = ͓1-methyl-1,3,5-triaza-7-phosphaadamantane͔ + ; X = Cl − , I − ͒ were investigated by electrospray mass spectrometry ͑ESI-MS͒, in flow-cell cyclic voltammetry, by microelectrodes, and by combined online electrochemistry and electrospray mass spectrometry ͑EC/ESI-MS͒ in dimethyl formamide solution. Coordination changes and the structures of the initial compounds and the products of the electrooxidation of the Ru͑II͒ complexes were traced by in situ EC/MS n 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 Ru͑II͒-Ru͑IV͒ centers. The electrochemical studies show that it is possible to tune the formal potentials for the oxidation of ͓CpRuL 2 X͔ 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 Ͻ PPh 3 Ͻ 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.The use of neutral water-soluble monodentate phosphines such as 1,3,5-triaza-7-phosphaadamantane ͑PTA͒ has received renewed interest in the recent literature due to its ability to solubilize transition metal complexes in the aqueous phase. This property has been used for aqueous phase or biphasic homogeneous catalysis of Rh, Ru, and Pd-PTA complexes, in tests as new drugs for tumor inhibition ͑Ru-and Pt-PTA͒ and in photoluminescent devices ͑Au-PTA͒. 1 Other interesting characteristics of PTA are the ability to bridge different transition metals both via P and N donor atoms, to create complex water soluble organometallic networks, 2 and to selectively functionalize either P or N, for example by attack from BH 3 . 3,4 Ru͑II͒, Rh͑I͒, and Rh͑III͒ complexes of N-methyl-PTA ͑PTA-Me͒ such as trans-͓RuI 4 ͑PTA-Me͒ 2 ͔, ͓RuI 2 ͑PTA-Me͒ 3 ͑H 2 O͔͒I 3 , and ͓RhI 4 ͑PTA-Me͒ 2 ͔I are active catalysts for the hydrogenation of cinnamaldehyde 5 at the C v O bond for Ru, and at the C v C double bond for Rh. Also these complexes were found to be active in DNA binding studies. 6 The synthesis of the new rhenium pentahydride complex ͓ReH 5 ͑PPh 3 ͒ 2 ͑PTA͔͒ and its characterization by X-ray diffraction analysis, variable temperature infrared ͑IR͒ and nuclear magnetic resonance ͑NMR͒ experiments, including T 1 analysis and protonation studies was also recently described. 7

The reaction of 4-hydroxycoumarin (I) with a variety of aromatic binucleophilic compounds is studied. Some of the new compounds obtained show antibacterial activity with benzodiazepinone (III) being the most effective one. -(HAMDI, N.; LIDRISSI, C.; SAOUD, M.; NIEVAS, A. R.; ZARROUK, H.; Chem. Heterocycl.