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This review focuses on the latest findings on the photochemical production of H2 catalyzed by heterometallic complexes.

Neutron scattering combined with ab initio calculations provides a powerful tool for studying metal complexes in different solvents and, particularly, in water. The majority of traditional characterization techniques in catalysis provide only limited information on homogeneous catalytic processes. Neutron scattering, on the other hand, thanks to its sensitivity to hydrogen atoms, and therefore water molecules, can be used to build detailed models of reaction paths and to observe, at a molecular level, the influence of solvent molecules on a catalytic process. In this Mini-Review we describe several examples on how neutron scattering combined with ab initio calculations can be used to examine the nature of the interaction of water molecules with catalytically active metal complexes in solution.

Complexes [Ru(η

Complexes [RuCp(Adeninate–κN9)(mPTA)2](Cl0.5)(CF3SO3)2.5·H2O (1·H2O), [RuCp(Guaninate-κN7)(mPTA)2](CF3SO3)2·H2O (2·H2O), [RuCp(Theophyllinate-κN7)(mPTA)2](CF3SO3)2·1.5H2O (3·1.5H2O) and [RuCp(Pur-κN)(mPTA)(PPh3)](CF3SO3) (4–6) (Pur = Adeninate, Guaninate, Teophyllinate; mPTA = N-methyl −1,3,5-triaza-7-phosphaadamantane) have been synthesized and characterized. Structure of complexes 1·H2O and 3·1.5H2O were determined by single-crystal X-ray diffraction. Solubility in water, Log P, electrochemical properties and antiproliferative activities of the complexes (against cisplatin-sensitive T2 and cisplatin-resistant SKOV3 cell lines) have been assessed and discussed.

The newly synthesized mer-trans-[RuCl2(OH2)(PTA)3] (1) is the first compound isolated in solid state containing the Ru(PTA)3-fragment (PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane). Dissolution of 1 in aqueous HCl leads to mer-[RuCl3(HPTA)3]Cl2 (2) which is stable in the dark but is transformed into fac-[RuCl3(HPTA)3]Cl2 (3) under visible light. Irradiation with visible light of an aqueous solution of 1 at room temperature or refluxing of the same solution in the dark leads to the formation of [{Ru(PTA)3}2(μ-Cl)3]Cl (4). The dinuclear complex 4 was also formed upon irradiation of solutions of PTA and various Ru(II)-complexes ([RuCl2(DMSO)4], [{RuCl2(η6-p-cymene)}2]) or cis-cis-trans-[RuCl2(DMSO)2(PTA)2]). All complexes were characterized by elemental analysis and NMR spectroscopy, furthermore solid state structures of 2·1.25H2O, 3·HCl·2H2O and 4·9H2O were also determined by single crystal X-ray diffraction. We have investigated the influence of the above photochemical processes on reduction of benzaldehyde and cinnamaldehyde with trans-[RuCl2(PTA)4] and cis-cis-trans-[RuCl2(DMSO)2L2] (L = PTA, (PTA-Me)CF3SO3, (PTA-Bn)Cl; Me = methyl, Bn = benzyl) complexes as catalysts. The effect of visible light on benzonitrile hydration with various Ru(II)-PTA catalysts is also reported.

The C–C coupling is the best strategy to obtain new organic molecules and building blocks from economical and abundant small molecules. Traditionally these reactions are accomplished in organic solvents, which are often dried before use as water molecules can react quickly with both the catalyst or the intermediate of the reactions, blocking the catalytic cycle. Nevertheless, the efforts of the researchers are providing new synthetic procedures in water that can substitute some of those, previously developed, “dry reactions”. In the last years, really useful processes to obtain C–C bonds in water were proposed. These reactions usually are catalysed with 4d-metals but also examples with metals of the first transition row were proposed. This review aims to summarize and order by types the C–C coupling catalytic reactions in water published during the last five years. The abundance of reactions and the significance of the published results shows that a long way is needed to achieve a good knowledge of catalytic C–C coupling reactions in water. Nevertheless, accomplish this objective can provide significant and valuable synthetic processes, more economical, cleaner, more selective, therefore friendlier and more respectful with nature.

The isomerization of 1-penten-3-ol into 3-pentanone catalyzed by [RuCp(H2O-κO)(PTA)2](CF3SO3) (1CF3SO3) (PTA = 1,3,5-triaza-7-phosphaadamantane) was studied and two water soluble ruthenium catalyst reaction intermediates were characterized. The main intermediate, the complex [RuCp(exo-2-1-penten-3-ol)(PTA)2](CF3SO3)·2H2O (exo- 2CF3SO3·2H2O) was isolated and characterized by NMR in solution and by single-crystal X-ray diffraction in solid state, constituting the first example of a fully characterized complex containing a coordinated 2-allylic alcohol and the first crystal structure for a water-soluble metal complex containing a 2-allyl ligand. NMR and Eyring analysis show the crucial involvement of water molecules both in the transformation of allylic alcohol into a ketone as well as in the concomitant isomerization of the exo-coordinated substrate into the endo conformer. DFT structure and bonding analyses are used to assess the relative stabilities of the isomers and how the metal drives the electronic distribution on the substrate.

Complexes [RuCp(Adeninate-κN9)(PTA)2] (1), [RuCp- (Guaninate-κN9)(PTA)2] (2), [RuCp(Theophyllinate-κN7)(PTA)2] (3), [RuCp(Adeninate-κN9)(PPh3)(PTA)] (4), [RuCp(Guaninate- κN9)(PPh3)(PTA)] (5) and [RuCp(Theophyllinate-κN7)(PPh3)(PTA)] (6) were synthesized and characterized by NMR spectroscopy, elemental analysis and FT-IR (PTA = 1,3,5-triaza-7-phosphaadamantane). Crystal structures of 1·H2O·3EtOH, 3·CH3COCH3 and 4·H2O were also determined by single-crystal X-ray diffraction. The antiproliferative activities of the complexes against cisplatin-sensitive T2 and cisplatin-resistant SKOV3 cell lines have also been evaluated. Theoretical studies were preformed to elucidate how the adeninate ligand is coordinated to the metal.

New coordination polymers based on two metal-containing moieties Ru&ndash, Ag are synthesized: Na[RuCpX(PTA)-&mu, (PTA)-1&kappa, P:2&kappa, 2N-AgX2]&infin, (X = Cl (1), Br (2), I (3)). Characterization is performed by NMR, UV-visible and FT-IR spectroscopy, optical-electron microscopy, and elemental analyses (C, H, N, S). Light scattering is employed to characterize the colloidal particles growth by polymer self-assembling. These structures are stable over a broad range of pH and exhibit thermally-driven swelling, thus resembling a typical thermosensitive hydrogel.

Isomerisation of allylic alcohols in water mediated catalytically by water soluble metal complexes is an elegant synthetic procedure for obtaining carbonyl compounds in a completely atom-economical ecobenign process with several useful applications in natural-product synthesis and in bulk chemical processes. This review is targeted to provide a general view of the goals obtained in isomerisation catalysis in water. Complexes that catalyze the isomerization of allylic alcohols in water, together with ligands and reaction conditions are compared with respect to yield, turnovers, rate and selectivity. A general overview of the mechanisms proposed for the isomerisation of allylic alcohols is also presented. Crystal structures and selected bond lengths are presented for the most representative catalytically active metal complexes.

The complexes [RuCp(8MTT-κ S) LL′] and [RuCp(8MTT-κ N7) LL′] (8MTT = 8-methylthio-theophyllinate; L,L′ = PTA, mPTA; L = mPTA, L′ = PPh 3 ; PTA = 1,3,5-triaza-7-phosphaadamantane, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane) have been investigated by DFT theoretical methods. Structures, infrared spectra and thermodynamical properties in gas phase, water and ethanol of the studied complexes have been determined at B3LYP/DZVP level of theory. Complexes [RuCp(8MTT-κ S )(PTA) 2 ] and [RuCp(8MTT-κ S )(mPTA)(PPh 3 )] + are slightly stabilized by favourable Gibbs free energy respect to [RuCp(8MTT-κ N7 )(PTA) 2 ] and [RuCp(8MTT-κ N7 )(mPTA)(PPh 3 )] + in gas phase while in water and ethanol the calculated Gibbs free energy showed that the 8MTT-κ S -complexes are quite more stable than the corresponding 8MTT-κ N7 -complexes. However, the [RuCp(8MTT-κ N7 )(mPTA) 2 ] 2+ is more stable than the corresponding κ S -complex in gas phase while in water remains less stable . These theoretical results are in agreement with obtained until now experimental results as two new 8MTT - κ S -complexes, [RuCp(8MTT-κ S )(mPTA)(PPh 3 )](CF 3 OSO 2 ) ( 1 ) and [RuCp(8MTT-κ S )(mPTA) 2 ]Cl(CF 3 OSO 2 )·1.5H 2 O ( 2 · 1.5H 2 O ) were synthesized and characterized by single crystal X-ray diffraction.

A new water soluble complex [RuCp(H2O-KO) (PTA)(2)](+) (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) has been synthesized and fully characterized by NMR and IR. The crystal structure of 1(CF3SO3)center dot 3.5H(2)O was characterized by single crystal X-ray determination. The catalytic activity of this complex was evaluated for the isomerisation of linear allylic alcohols from 3-buten-2-ol to 1-octen-3-ol into the correspondent ketones under both an inert atmosphere and in air, using as solvents: water, the substrate, mixtures of water/substrate, MeOH and mixtures of MeOH/water. An isomerization experiment on a mixture of all the studied allylic alcohols was also carried out.

New water soluble {CpRu} complexes with formula [RuCpX(L1)(L2)]n+ (L1, L2 = PPh3, mTPPMS (meta-triphenyphsphine monosulfonate), PTA (1,3,5-triaza-7-phosphaadamantane), mPTA (N-methyl-1,3,5-triaza-7-phosphaadamantane)) were synthesized and characterized by elemental analytical, IR and NMR spectroscopy. Complexes [RuClCp(PPh3)(mPTA)](OTf) (3·OTf), [RuCpI(PPh3)(mPTA)]·2I·EtOH (5·I·EtOH)·and [RuCpBr(PTA)2]·3.5H2O (6·3.5H2O) were also characterized by single crystal X-ray diffraction. The NMR spectra of the complexes are in agreement with their composition, indicating also that their solid state structure is maintained in solution. These results are integrated in a thorough overview of preparative routes, structural composition and solubility of {CpRu} complexes containing water-soluble phosphanes.

Synthesis, characterization and the antiproliferative activity of a new bimetallic complex [RuCp(PPh3)2-μ-dmoPTA-1κP:2k2N,N′-CoCl2]OTf·0.25H2O are described. The stability of the complex was studied under air and N2 atmospheres and in CDCl3, DMSO, water and the cell culture medium, at room temperature and 40 °C. The complex showed an enhanced antiproliferative activity (up to six-fold) when compared with its parent complex [RuCp(PPh3)2(HdmoPTA)]2+ against human lung, cervix, breast, and colon solid tumor cell lines.

Metal-free and metallophthalocyanines 3–10 carrying four coumarins group on the periphery were prepared by cyclotetramerisation of a new precursor, namely 4-(4-Methyl-2-oxo-2H-chromen-7-yloxy)-phthalonitrile 1 and 4-(2-Oxo-2H-chromen-7-yloxy)-phthalonitrile 2 in the presence of the corresponding divalent metal salts (Zn (II), Cu(II) and Co(II). The aggregation behaviors of the unmetalled 3 and metallophthalocyanines 5 were investigated. The novel phthalonitrile derivatives 1–2 were synthesized by the reaction between 4-nitrophthalonitrile with 7-hydroxy-4-methylcoumarin and 7-hydroxycoumarin respectively in polar aprotic solvents (DMF or DMSO) in the presence of dry K2CO3 as base catalyst. The characterization of the new products involved a combination of methods including elemental analyses, IR, UV–vis, 1H NMR, 13C NMR and mass spectroscopies. Most of the new compounds 3–10 exhibited important antimicrobial activity.

The water soluble complexes cis-[Ru(bpy)2(PTA)2]Cl2 (1Cl2), cis-[Ru(bpy)2(PTA)2](PF6)2 (1(PF6)2), trans-[Ru(bpy)2(PTA)2](CF3SO3)2 (2(CF3SO3)2), cis-[Ru(bpy)2(PTA)(H2O)](CF3SO3)2 (3(CF3SO3)2), cis-[Ru(bpy)2(PTAH3)(H2O)](CF3SO3)5 (4(CF3SO3)5), cis-[Ru(bpy)2(PTAH3)2](CF3SO3)8 (5(CF3SO3)8) and trans-[Ru(bpy)2(PTAH3)2](CF3SO3)8 (6(CF3SO3)8) have been synthesized and characterized by elemental analysis, NMR and IR spectroscopy. The crystal structures of 1(PF6)2, 2(CF3SO3)2, 4(CF3SO3)5 were obtained by single-crystal X-ray diffraction. Both experimental and computational techniques were utilized to perform a thorough analysis of the structural and electronic properties of the complexes 1 and 2 in water in both the deprotonated and protonated state and under N2 and air. UV/Visible absorbance spectroscopy revealed the sensitiveness of complex 1 and 2 to the pH. Both Ligand-to-Metal Charge Transfer (LMCT) and Metal-to-Ligand/Ligand-to-Ligand Charge Transfer (MLCT/LLCT) transisions were observed in the absorption spectrum. Luminescence studies showed that these complexes are active fluorescence compounds, despite the presence of monofosfines in their structure. The pH sensitiveness of the emission band of both complexes was studied. The photohydrolisis of 1 and 2 in acid water solution was also studied, showing that both complexes release a PTA molecule under selective irradiation in acidic water to give rise to the complex 4. Cyclic voltammetry showed that, in water, irreversible anodic oxidation corresponding to the Ru(II)/Ru(III) redox process occurs for 1, whereas for 2 the process is quasi-reversible. In DMF the redox Ru(II)/Ru(III) wave for both complexes are irreversible and occur at lower potential than in water.

This minireview summarizes some of the most significant findings published in the last years on metal complexes containing PTA and PTA derivatives ligands such as dmoPTA, with antiproliferative activity [PTA = 1,3,5-triaza-7-phospha- adamantane; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[ 3.3.1]nonane (dmoPTA)]. Comments on other biological properties of the complexes are also included.

Despite the large interest by both industrial and academic chemists to develop a safe and environmentally acceptable process to functionalize white phosphorus, only few but significant steps have been developed in the last years. New experimental results and theoretical studies provide indeed obust evidence that different metal complexes are really capable of mediating the formation of P C bond starting from P4 and organic reagents and that even catalytic processes accomplishing the direct phosphorylation of alcohols or other organic substrates may be achieved via the intermediacy of a suitable metal complex. Nevertheless and in spite of the relevant findings achieved so far and of the impressive variety of metal complexes containing P atoms and polyphosphorus, Px, units which have been synthesized and characterized up to now, the original target of the direct (catalytic) phosphorylation of elemental phosphorus remains still unsolved. In this chapter the more recent results paving the way to the direct functionalization of white phosphorus are presented and discussed.

The catalytic activities of [RuClCp(PTA)2] (1) and [RuCp(PTA)2 (H2O-κO)]OTf (2) were assessed for the redox isomerization of the cyclic allylic alcohol 2-cyclohexenol into cyclohexanone in water and biphasic media. Complex 2 showed unprecedented good TONs for the studied conversion both in water (TON = 647) and in the biphase of cyclohexene/H2O (TON = 3420) while 1 showed a lower but also good activity (water TON = 95, biphasic TON = 100). The catalytic reaction intermediate [RuCp(PTA)2(η2-C6H9OH)] CF3SO3 (3) was synthesized and characterized using NMR.

We present the internal structure and dynamics of novel coordination polymers based on two metal-containing moieties Ru-X (X: Ag, Au, Co), bridged through the phosphine PTA (3,5,7-triaza-phosphaadamantane). X-ray scattering gives the heterometallic polymer organization. Quasi-elastic neutron scattering measurements over a broad temperature range show a transition from vibrational Debye-Waller behavior to a more dynamically active state, but with rather localized motions, coinciding with the loss of structural water at around room temperature. Light scattering reveals that the polymers self-associate to form stable micro-particles in aqueous solution with a thermally driven volume transition. This is described by the Flory theory for polymers in solution, in which the polymer solvency is calculated as a function of the temperature. Polymer self-organization is further studied by small-angle neutron scattering and electron microscopy. A polymer parallel-plane model with gaps controlled by the environmental temperature is proposed.

We study the intermediate of the reaction between a ruthenium complex and 1-propen-3-ol in water using an atomistic approach for gaining information about the conformation and dynamics of complex molecules in aqueous solution, which combines density-functional-theory-based ab initio molecular dynamics and neutron scattering data based on empirical potential structure refinement simulations. We apply our method to the study of the water-soluble η2-allylic complex [RuCp(exo-η2- CH2 CH−CH2−OH)(PTA)2]+ (2) (PTA = 1,3,5-triaza-7- phosphaadamantane), an important intermediate in the isomerization of 1-propen-3-ol into propanal catalyzed by {RuCp(H2O- κO)(PTA)2}+. We identify the factors responsible for the stabilization of a specific conformer of 2 in water solution and we examine the involvement of water molecules in the formation of this species. In particular, we show that long-lived (ca. 10 ps) bonded chains of water molecules play a crucial role in influencing the conformation and, potentially, the chemical reactivity of 2.

The backbone hetero-organometallic polymer trans-{[RuCp(PTA)2-μ-CN-RuCp(PTA)2-μ-CoCl3]}n·(DMSO)n (1·DMSO) has been synthesized and transformed into cis-{[{RuCp(PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2}- μ-CoCl3]}n·{[RuCp(PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2]Cl}0.5n·(15H2O)n (2·15H2O) by addition of water to crystallization media (PTA = 1,3,5-triaza-7-phosphaadamantane). The new polymer 2·15H2O presents a nano-channeled molecular packing with pores filled by water molecules. The crystal structures of 1·DMSO and 2·15H2O and the transformation process are herein presented and discussed.

The catalytic activity of [RuClCp(HdmoPTA)(PPh3)](OSO2CF3) (1) and the dimeric complexes [RuClCp(PPh3)-μ-dmoPTA-1κP:2κ2N,N'-MCl2] (M = Ni (2), Co (3), Zn (4)) for the isomerization in water under Ar and ambient atmosphere of 1-octen-3-ol, 1-hepten-3-ol and 1-hexen-3-ol was investigated. A detailed study was devoted to the catalytic activity under Ar of 1 for the isomerization of 1-octen-3-ol.

Complexes [Ru( N , N , N -tris(benzimidazole-2-yl-methyl)amine-κ N , N ′, N ‴)Cl(PPh 3 )]Cl ( 1 ), [Ru( N , N -bis(benzimidazole-2-yl-methyl)hydroxyethylamine-κ N , N ′, N ‴)Cl(PPh 3 )]Cl ( 2 ) and [Ru( N , N , N -tris(2-aminoethyl)amine-κ N , N ′, N ‴)Cl(PPh 3 )]Cl ( 3 ) were synthesized by reaction of [Ru(PPh 3 ) 3 Cl 2 ] with N , N , N -tris(benzimidazole-2-yl-methyl)amine ( L 1 ), N , N -bis(benzimidazole-2-yl-methyl)hydroxyethylamine ( L 2 ) and N , N , N -tris(2-aminoethyl)amine ( L 3 ), respectively. The water soluble complex [Ru( N , N , N -tris(benzimidazole-2-yl-methyl)amine-κ N , N ′, N ‴)Cl(PTA)]Cl ( 4 ) was obtained by reaction of 1 with PTA (1,3,5-triaza-7-phosphinoadamantane). Complexes were characterized by IR, NMR and elemental analysis. The structure of 1 was determined by single crystal X-ray diffraction analysis. Photo- and electro-chemical behaviours evolution of the complexes were also done. The structural and electronic properties of 1 , 2 and 3 were studied by DFT and DFT-TDDFT.

The water-soluble backbone heterometallic polymer {[(PTA)2 CpRu-μ-CN-RuCp(PTA)2 -μ-NiCl3 ]}n (2) is synthesized using a reproducible and robust method and fully characterized by X-ray single crystal diffraction. The Ru-Ru-Ni polymer is found to be stable in the solid state and soluble in water. Nuclear magnetic resonance (NMR) and light scattering studies show that the polymer is stable in water for several days in air.

A new family of linear metal polymers of formula [M(isn-κNpy)4(μ-SiF6-κF,F′)]n (M = Cu, Co, Ni; isn = isonicotinamide) have been synthesized and characterized. The authenticities of these polymers were characterized by elemental analysis, IR and electronic absorption spectroscopy and magnetic susceptibility, which suggested that all the three complexes possess a similar structure. The crystal structure of the Cu-complex was determined by single crystal X-ray diffraction, showing that the compound is a backbone metal chain in which the metals are linked by a SiF62− bridges.

Simultaneous Raman spectroscopy and inelastic neutron scattering have been used to obtain structural information about the isomeric metal-organic polymers trans-[{RuCp- (PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2}-μ-CoCl3]n·(DMSO)n (2), cis- {[{RuCp(PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2}-μ-CoCl3]}n·{[RuCp- (PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2]Cl}0.5n·(15H2O)n (3) and {[{RuCp(PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2}-μ-CoCl3]}n·{[RuCp- (PTA)2-μ-CN-1κC:2κ2N-RuCp(PTA)2]Cl}0.5n (4) (PTA = 1,3,5-triaza- 7-phosphaadamantane). Despite the complexity of the compounds, the combination of both techniques has been useful to understand the conformation-dependent fingerprint of the polymers and, at the same time, to obtain preliminary information about how the water molecules are confined in the structural channels of 3.

Two novel ruthenium complexes are synthesized, photo-characterized and tested as photosensitizers in dyesensitized solar cells (DSCs): [RuCl2(mPTA)3(H2O)](CF3SO3)3 (C1) (m: methyl; PTA: 3,5,7-triaza-phosphaadamantane) and [Ru(C=C=CPh2)Cp(PTA)(PPh3)](CF3SO3) (C2). The complexes are soluble in organic solvents and, interestingly, in water, which makes them useful for water-based photochemical processes. They possess excellent photon-absorption over a wide range of the spectrum with intense peaks at ∼ 330 nm for both sensitizers. A second peak is found for C2 at 525 nm, wider than the corresponding to the N719 standard dye. DSCs using these sensitizers are evaluated against different electrolytes. The solar cell performance was similar for both complexes and strongly dependent on the electrolyte nature, with a maximum conversion efficiency of 0.32% for the iodide/triiodide electrolyte.

Synthesis, characterization and the antiproliferative activity of a new bimetallic complex [RuCp(PPh

A new water soluble complex [RuCp(H

The water-soluble complex [RuClCp(PPh3)(mPTA)](CF3SO3) reacts with the thiopurines, bis(S-8-thiotheophylline)methane (MBTTH2), 1,2-bis(S-8-thiotheophylline)ethane (EBTTH2), and 1,3-bis(S-8-thiotheophylline)propane (PBTTH2), to lead to the binuclear ruthenium(II) complexes [{RuCp(PPh3)(mPTA)}2-μ-(L-κS7,S′7)](CF3SO3)2 where (L = MBTT2− (1), EBTT2− (2), and PBTT2− (3)). All the complexes have been fully characterized by elemental analysis, IR, and multinuclear 1H, 13C{1H}, and 31P{1H} NMR spectroscopy. The cyclic voltammetry of the complexes is characterized by two one-electron oxidative responses (RuII–RuII/RuIII–RuII; RuIII–RuII/RuIII–RuIII) that increase their redox potential when the bis(8-thiotheophylline)-alkyl-bridge growths. The reactivity against DNA and partition coefficient of the complexes were also determined.

White phosphorus (P4) is a small molecule that is mainly used as a starting material for the large-scale synthesis of most of the suitable phosphorus derivatives. The process starts with the direct reaction of P4 with Cl2, and the resulting phosphorus chloride is further treated with the adequate organic substrate. This industrial process is very primitive, and for economic and environmental reasons the first oxidation step should be avoided. The observation that the conversion of white P4 to the red allotrope is accelerated by ultraviolet light showed that the P4 molecule is able to be activated by electromagnetic radiation. Metal complexes can also mediate the functionalization of P4. The participation of electromagnetic radiation in the reactions that involve P4 and metal complexes has provided new procedures for obtaining new and interesting compounds that contain phosphorus atoms. Very significant and interesting reviews have summarized, classified and discussed the reactivity of P4 but until now none of them have distilled the relationship between white phosphorus and electromagnetic radiation.

The study of an aqueous solution of [RuCp(PTA)2-μ-CN-1κC:2κ(2)N-RuCp(PTA)2](CF3SO3) by neutron and X-ray diffraction revealed surprising details as to how the water molecules interact with the complex and affect its properties. The present communication demonstrates the applicability of sophisticated scattering techniques in combination with theoretical calculations to the study of coordination compounds in aqueous solution.

The new water-soluble palladium(II) complexes Na2{trans-[PdCl2(mTPPMS-κP)2]} (1), (CN4H7)Na{trans-[PdCl2(mTPPMS-κP)2]} (2) and the 2D polymer trans-{Pd-μ-[mTPPMS-1κP:2κO-Na1/2(H2O)]-μ-[mTPPMS-1κP:2κO′-Na′1/2(H2O)]-μ-[8TTH-1κS:2κO6–Na1/2(H2O)]-μ-[8TTH-1κS:2κO6-Na′1/2(H2O)]}n (3) {mTPPMS = Ph2P[3-OS(O)2C6H4]–; 8-TTH = 8-thiotheophyllinate} have been synthesized and characterised by NMR and IR spectroscopy as well as elemental analysis. The crystal structures of 2 and 3 were determined by X-ray diffraction. The binding properties of the new hydrosoluble palladium complexes towards DNA were studied by the mobility shift assay, which showed that complex 1 is more active than cisplatin towards DNA.

International audience; Phosphorhydrazone dendrimers ended by PTA (1,3,5-triaza-7-phosphaadamantane) derivatives are used for the complexation of ruthenium. The corresponding complexes, either isolated (synthesized ex situ, i.e. preformed) or generated in situ are used as catalysts for the hydration of phenylacetylene in various conditions (ex situ or in situ, quantities, temperature, duration, co-catalyst or not, recycling). The same preformed complexes are tested for their interaction with supercoiled DNA, to afford relaxed DNA.

Thiopurines bis(S-8-thiotheophylline)methane (MBTTH2), 1,2-bis(S-8-thiotheophylline)ethane (EBTTH2), and 1,3-bis(S-8-thiotheophylline)propane (PBTTH2) were reacted with [RuClCp(mPTA)2](CF3SO3)2 in water to afford the bis-ruthenium complexes [{RuCp(mPTA)2}2-μ-(L-κN7,N′7)](CF3SO3)4 (1: L = MBTT; 2: L = EBTT; 3: L = PBTT), which have been characterized by elemental analysis, IR, and multinuclear NMR (1H, 13C{1H}, 31P{1H} and 19F{1H}) spectroscopy). Diffusion experiments for 1 were carried out. Proposed structures for the three complexes were also supported by theoretical calculations. Cyclic voltammetry showed that these complexes are characterized by two one-electron irreversible oxidative response (RuII – RuII/RuIII – RuII; RuIII – RuII/RuIII – RuIII). Complexes showed poor antiproliferative activity against cisplatin-sensitive T2 human cell line and the cisplatin-resistant SKOV3 cell line.

The complex [RuCp(PPh3)2(HdmoPTA)](OSO2CF3)2 (2; HdmoPTA = 3,7-H-3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) was synthesized and characterized. Its crystal structure was determined by single-crystal X-ray diffraction. The complex showed a more potent antiproliferative activity than cisplatin against a representative panel of human cancer cells.