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New water soluble {CpRu} complexes with formula [RuCpX(L 1 )(L 2 )] n+ (L 1 , L 2 = PPh 3 , 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(PPh 3 )(mPTA)](OTf) ( 3·OTf ), [RuCpI(PPh 3 )(mPTA)]·2I·EtOH ( 5·I·EtOH )·and [RuCpBr(PTA) 2 ]·3.5H 2 O ( 6·3.5H 2 O ) 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. [ABSTRACT FROM AUTHOR]

The water-soluble backbone heterometallic polymer {[(PTA)2CpRu-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. [ABSTRACT FROM AUTHOR]

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-?-(L-?S7,S?7)](CF3SO3)2where (L = MBTT2?(1), EBTT2?(2), and PBTT2?(3)). All the complexes have been fully characterized by elemental analysis, IR, and multinuclear1H,13C{1H}, and31P{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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of three novel heterobimetallic derivatives of general formula [RuClCp(PPh3)-μ-dmoPTA-1κP:2κ2N,N′-MCl2] (M = Co (1), Ni (2) and Zn (3), dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) are described. The sizes of their diffusing units are in agreement with the solid-state structures of 2 and 3, supporting a similar solid-state structure for complex 1. The diamagnetic ruthenium–zinc derivative 3 was fully characterized in solution at 193 K by NMR. Electrochemical properties of the complexes were investigated by cyclic voltammetry, supporting the influence of the {MCl2} moiety on the electronic properties of the Ru-unit. For the three complexes the GI50 values were in the range 0.8–6.5 μM and comparable to those of the standard anticancer drug cis-platin in the same cell lines. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Abstract: The behaviour of [RuClCp(mPTA)2](OSO2CF3)2 (1) in water solution vs. the pH was studied. Complex 1 is stable in neutral and acidic water solution while in basic water solution another complex, [RuCp(OH-κO)(mPTA)2](OSO2CF3)2·(C4H10O) (2), is obtained. Complexes [RuCp(mPTA)2(L)]·X n (L=H2O-κO, X= −OSO2CF3, n =3 (3); L=Cl, , n =2 (4); L=DMSO-κS, X= −OSO2CF3, n =3 (5)) were also obtained. All presented complexes were characterised by IR and multinuclear (1H, 13C{1H}, 19F{1H}and 31P{1H}) NMR spectroscopy. Improved synthesis for 1, the thermal analysis of complexes 1–3 and the crystal structure of the complexes 1 and 5 are also presented. [Copyright &y& Elsevier]