Novel polarised molecular wires based on transition metal complexes of di4-pyridylheterocycles spacers bridging ligands

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Ruthenium metallodendrimers based on Nitrile-functionalized Poly(alkylidene imine)s

Publication . Ornelas, Cátia; Vertlib, Viatcheslav; Rodrigues, João; Rissanen, Kari

The preparation of the first- and second-generation of nitrilefunctionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(η5-C5H5)(PPh3)2Cl] peripherally attached is described. The reaction of N,N -bis(cyanomethyl)piperazine (1), N,N -bis[N ,N -bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,N ,N -tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(η5-C5H5)(PPh3)2Cl] (4) in the presence of TlPF6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel quantitative method to solidify and chromatographically purify the otherwise semi-liquid nitrile-functionalized poly(alkylidene imine) dendrimers. The compounds were fully characterized by IR and 1H, 13C, and 31P NMR spectroscopy, and mass spectrometry. These dendrimers represent the first example of the utilization of nitrile-functionalized poly(alkylidene imine)s as cores in the preparation of metallodendrimers.

2006Journal article

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cis-Aquabis[bis(diphenylphosphino)ethane-j2P,P000]chlororuthenium(II) hexafluorophosphate dichloromethane sesquisolvate hemihydrate

Publication . Russo, Luca; Figueira, João; Rodrigues, João; Rissanen, Kari

2006Journal article

Open access

A trinuclear aqua cyano-bridged ruthenium complex [{(η5-C5H5)(PPh3)2Ru(μ-CN)}2RuCl2(PPh3)(H2O)]PF6: synthesis, characterization and crystal structure

Publication . Vertlib, Viatcheslav; Figueira, João; Mesquita, José; Rodrigues, João; Nättinen, Kalle; Rissanen, Kari

The organometallic trinuclear aqua cyano-bridged complex [{(η5-C5H5)(PPh3)2Ru(µ-CN)}2RuCl2(PPh3)(H2O)]PF6 (1), in which the fragment [RuCl2(PPh3)(H2O)] acts as a bridge and an acceptor group between the two terminal cyclopentadienyl ruthenium cyano moieties, was isolated in moderate yield from the reaction of [(η5-C5H5)(PPh3)2RuCN] with [RuCl2(PPh3)3] in THF. To the best of our knowledge, compound 1 is one of the few examples of a trinuclear array of ruthenium fragments bridged by the nitrogen atom of the –C N– group (Ru–C N–Ru –N C–Ru) with a Ru-coordinated water molecule. The new aqua complex was structurally characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, elemental analysis, single-crystal X-ray diffraction, and cyclic voltammetry. The title complex crystallizes in a triclinic unit cell a = 17.3477(6) Å, b = 17.8551(5) Å, c = 18.2460(7) Å, α = 95.693(2)°, β = 111.648(2)°, and γ = 97.839(2)° in the space group P1 ¯ with Z = 2.

2007Journal article

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cis-[Bis(diphenylphosphino)ethane-κ2P,P′]dichlororuthenium(II) dichloromethane disolvate

Publication . Russo, Luca; Figueira, João; Rodrigues, João; Rissanen, Kari

2006Journal article

Open access

4,4′-[Thiophene-2,5-diylbis(ethyne-2,1-diyl)]dibenzonitrile

Publication . Figueira, João; Vertlib, Viatslav; Rodrigues, João; Nättinen, Kalle; Rissanen, Kari

In the solid state, the title compound, C(22)H(10)N(2)S, forms centrosymmetric dimers by pairs of non-classical C-H⋯S hydrogen bonds linking approximately coplanar mol-ecules. The benzene ring involved in this inter-action makes a dihedral angle of only 7.21 (16)° with the thio-phene ring, while the other benzene ring is twisted somewhat out of the plane, with a dihedral angle of 39.58 (9)°. The hydrogen-bonded dimers stack on top of each other with an inter-planar spacing of 3.44 Å. C-H⋯N hydrogen bonds link together stacks that run in approximately perpendicular directions. Each mol-ecule thus inter-acts with 12 adjacent mol-ecules, five of them approaching closer than the sum of the van der Waals radii for the relevant atoms. Optimization of the inter-stack contacts contributes to the non-planarity of the mol-ecule.

2008Journal article

Open access