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The new water soluble ruthenium complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesised and characterised. Their evaluation as regioselective catalysts for hydrogenation of unsaturated ketones in aqueous biphasic conditions and as cytotoxic agents towards the TS/A adenocarcinoma cell line is briefly presented.

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.

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.

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Dedicated to Professor Otto J. Scherer on the occasion of his 68th birthday A critical survey of the coordination chemistry of white phosphorus illustrating the metalmediated degradation of the P 4 tetrahedron is presented. The underlying principles to account for the activation and stepwise fragmentation of this molecule in the presence of transition metal complexes are presented with emphasis given to mechanistic aspects. A collection of 31 P-NMR spectral data for the known polyphosphorus P x compounds (x £ 4) is also presented and briefly commented.

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 ...