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  • Publication
    Métadonnées seulement
    Conversion of ethylene into ethylidyne on a mixed-metal cluster: synthesis and structure of IrRu4(CO)(15)(mu(4)-CH3)
    (1999)
    Haak, Susanne
    ;
    Neels, Antonia
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    ;
    The thermal reaction of the tetranuclear cluster HIrRu3(CO)(13) with ethylene in hexane (90 degrees C, 2 bar) affords, in addition to H3IrRu3(CO)(12), the pentanuclear cluster HIrRu4(CO)(15)(mu(4)-C-CH3) (1) in which the ethylidyne ligand is coordinated through a carbon atom to the four ruthenium atoms in the IrRu4 core. In this reaction, the CH2=CH2 molecule has been transformed into a C-CH3 moiety coordinated as a mu(4)-ligand to the cluster. (C) 1999 Elsevier Science S.A. All rights reserved.
  • Publication
    Métadonnées seulement
    Metal-framework degradation reactions of the mixed-metal cluster anions [M3Ir(CO)(13)](-) (M=Ru, Os) with bis(diphenylphosphino)methane and with tricyclohexylphosphine: synthesis and structure of HRu2Ir(CO)(5)(dppm)(3), HRu2Ir(CO)(6)(PCy3)(3), H2Os2Ir2(CO)(10)(PCy3)(2) and H3Os3Ir(CO)(8)(PCy3)(3)
    (1999)
    Haak, Susanne
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    ;
    Neels, Antonia
    ;
    The mixed-metal cluster anions [M3Ir(CO)(13)](-) (M=Ru, Os) react in methanol under metal-framework degradation with bis(diphenylphosphino)methane (dppm) or tricyclohexylphosphine (PCy3) to give a series of neutral tri- and tetranuclear mixed-metal clusters. The reaction of [M3Ir(CO)(13)](-) (M=Ru, Os) with dppm leads to the phosphine-substituted hydrido derivatives HRu2Ir(CO)(5)(dppm)(3) (1) and HOs2Ir(CO)(5)(dppm), (2), respectively. The two 48e clusters show a triangular arrangement of the M2Ir skeleton. The dppm ligands are coordinated in bridging positions over each metal-metal edge; the hydride is bonded terminally to the iridium atom. Cluster degradation is also observed by treating [Ru3Ir(CO)(13)](-) with PCy3 in methanol, giving the highly electron-deficient (44e) mixed-metal cluster HRu2Ir(CO)(6)(PCy3)(3) (3). The reaction of the osmium homologue [Os3Ir(CO)(13)](-) with PCy3 under the same conditions leads to a mixture of the neutral tetranuclear clusters H2Os2Ir2(CO)(10)(PCy3)(2) (4) and H3Os3Ir(CO)(8)(PCy3)(3) (5). Both clusters, 4 and 5 still have a tetrahedral metal core like the starting cluster anion but in 4 an osmium atom has been replaced by an iridium atom. The molecular structures of 1, 3, 4 and 5 were confirmed by single-crystal X-ray structure analyses. (C) 1999 Elsevier Science Ltd. All rights reserved.
  • Publication
    Métadonnées seulement
    New Ru-3(CO)(12) derivatives with bulky diphosphine ligands: synthesis, structure and catalytic potential for olefin hydroformylation
    (2001)
    Diz, Enrique Lozano
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    Neels, Antonia
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    ;
    The diphosphine clusters Ru-3(CO)(10)(dcpm) (1) and Ru-3(CO)(10)(F-dppe) (2) as well as the bis(diphosphine) clusters Ru-3(CO)(8)(dcpm)(2) (3) and Ru-3(CO)(8)(F-dppe)(2) (4) have been synthesised from Ru-3(CO)(12) and the bulky diphosphines 1,2-bis[bis(pentafluorophenyl)phosphino]ethane (F-dppe) and bis(dicyclohexylphosphino)methane (dcpm). While the single-crystal X-ray structure analyses of 1, 2 and 3 show the expected mu (2)-eta (2) coordination of the diphosphine ligands, that of 4 reveals an unusual structure with one mu (2)-eta (2)-diphosphine and one mu (1)-eta (2)-diphosphine ligand. The clusters 1-4 catalyse the hydroformylation of ethylene and propylene to give the corresponding aldehydes, 2 showing higher activities than those observed for Ru-3(CO)(12) and Ru-3(CO)(10)(dppc). (C) 2001 Elsevier Science Ltd. All rights reserved.
  • Publication
    Métadonnées seulement
    Reactions of the cluster anion [HRu3(CO)(11))](-) with dicyclohexylphosphine: Synthesis and molecular structure of H2Ru3(CO)(8)(PCy2)(2) and H2Ru3(CO)(6)(PCy2)(2)(HPCy2)(2)
    (2001) ;
    Godefroy, Isabelle
    ;
    Faure, Matthieu
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    Neels, Antonia
    ;
    The cluster anion [HRu3(CO)(11)](-) (1) reacts with dicyclohexylphosphine in THF solution to give the anionic derivative [HRu3(CO)(8)(PCy2)(2)](-) (2), protonation of which yields the neutral cluster H2Ru3(CO)(8)(PCy2)(2) (3) and, in the presence of excess phosphine, HRu3(CO)(7)(PCy2)(3) (4). In protic methanol as reaction medium, the reaction of 1 with HPCy2 gives directly the neutral complex H2Ru3(CO)(6)(PCy2)(2)(HPCy2)(2) (5). together with 4. The single-crystal structure X-ray analysis of 3 shows a closed triangular Ru, framework. Tho electron count is in accordance with the EAN rule, but the structure analysis of 5 reveals an open, almost linear Ru, skeleton, which is electron-deficient with respect to the EAN rule.
  • Publication
    Métadonnées seulement
    Reactions of the cationic complex [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(3)](+) with nitrogen-containing heterocycles in aqueous solution
    (1998)
    Jahncke, Manfred
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    Neels, Antonia
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    ;
    The dinuclear cation [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(3)](+) (1) reacts in aqueous solution with pyrazole and 4-methylpyrazole to give the bispyrazolato complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N2C3H2R)(2)](+) (R = H: 2, R = Me: 3). The reaction with 1,2,4-triazole results in the formation of the bistriazolato complex [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](+) (4) Successive protonation of the triazolato ligands in 4 leads to the complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),-N3C2H2)(mu(2)-eta(1),eta(1 )-N3C2H3)](2+) (5) and [(eta(6)-C6Me6)(2)RU2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](3+) (6). The reaction of 1 with 1,2,3-triazole gives a 1:1 mixture of the bistriazolato complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](+) with parallel (7a) and anti-parallel (7b) coordination of the triazolato ligands. The single-crystal X-ray structure analyses of 2 (hexafluorophosphate salt) and 4 (tosylate salt) reveal for both complex types a ruthenium-ruthenium backbone being bridged by the two heterocyclic ligands with the N-N axis coordinated in a mu(2)-eta(1),eta(1)-fashion. A single-crystal X-ray structure analysis of title complex 1 (hexafluorophosphate salt) confirms the presence of three bridging hydride ligands with a Ru-Ru distance of only 2.47 Angstrom. (C) 1998 Elsevier Science S.A. All rights reserved.
  • Publication
    Métadonnées seulement
    The novel sequence Diels-Alder reaction/Ireland-Claisen rearrangement applied to acyclic dienophiles: New insights into the selectivity of the Ireland-Claisen rearrangement
    (1999-1-12)
    Velker, Joerg
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    Roblin, Jean Philippe
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    Neels, Antonia
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    Tesouro, Ana
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    Klaerner, Frank-Gerrit
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    Gehrke, Jan-Stefan
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    The new dienes 4a-d, 7 and 11 reacted in good yields with acyclic dienophiles like methyl acrylate and diethyl fumarate in the tandem process Diels-Alder reaction/Ireland-Claisen rearrangement. Analysis of the relative configuration of products 5, 6, 8-10 and 12 indicated that preference for the chair or boat transition state of the Ireland-Claisen rearrangement is strongly influenced by the relative configuration of the substituents of the cyclohexene ring.
  • Publication
    Métadonnées seulement
    1,4-Bis(hex-yloxy)-2,5-diiodo-benzene
    (2010) ; ;
    Sereda, Olha
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    Neels, Antonia
    ;
    The centrosymmetric title compound, C(18)H(28)I(2)O(2), crystallized in the monoclinic space group P2(1)/c with the alkyl chains having extended all-trans conformations, similar to those in the centrosymmetric bromo analogue [Li et al. (2008 (black right triangle)). Acta Cryst. E64, o1930] that crystallized in the triclinic space group P. The difference between the two structures lies in the orientation of the two alkyl chains with respect to the C(aromatic)-O bond. In the title compound, the O-C(alk-yl)-C(alk-yl)-C(alk-yl) torsion angle is 55.8 (5)°, while in the bromo analogue this angle is -179.1 (2)°. In the title compound, the C-atoms of the alkyl chain are almost coplanar [maximum deviation of 0.052 (5) Å] and this mean plane is inclined to the benzene ring by 50.3 (3)°. In the bromo-analogue, these two mean planes are almost coplanar, making a dihedral angle of 4.1 (2)°. Another difference between the crystal structures of the two compounds is that in the title compound there are no halide(midline ellipsis)halide inter-actions. Instead, symmetry-related mol-ecules are linked via C-H(midline ellipsis)? contacts, forming a two-dimensional network.
  • Publication
    Métadonnées seulement
    Carbon-carbon coupling reactions of but-2-yne on a triruthenium framework: synthesis and molecular structure of Ru-3(CO)(7)[NS(O)MePh] (HCMeCMeCMeCMeCO) and Ru-3(CO)(8)(CMeCMeCMeCMe)
    (1999)
    Ferrand, Vincent
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    Neels, Antonia
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    ;
    The cluster HRu3(CO)(9)[NS(O)MePh] (1) reacts with two equivalents of MeC=CMe in tetrahydrofuran at 60 degrees C to give the dienonyl derivative Ru-3(CO)(7)[NS(O)MePh] (HCMeCMeCMeCMeCO) (2), along with an isomer mixture of Ru-3(CO)(8)[NS(O)MePh] (HCMeCMe) (3). At 100 degrees C, the same reaction gives rise to the formation of the diendiyl cluster Ru-3(CO)(8)(CMeCMeCMeCMe) (4). The single-crystal structure analyses reveal for 2 a closed Ru-3 skeleton and for 4 an open Ru, framework. (C) 1999 Elsevier Science S.A. All rights reserved.
  • Publication
    Métadonnées seulement
    A cluster containing a pyrazole ligand: [Ru3(?-H)(?-N2C3H3)(CO)10]
    (2002)
    Diz, Enrique Lozano
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    Neels, Antonia
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    ; ;
    The title cluster decacarbonyl-1?4C,2?3C,3?3C-?-hydrido-2:3?2H:H-?-pyrazolyl-2:3?2N1:N2-triangulo-triruthenium, [Ru3(?-H)(?-C3H3N2)(CO)10], which contains a pyrazole ligand, was synthesized and characterized, both spectroscopically and crystallog., as a cyclohexane solvate. Crystals are monoclinic, space group I2/a, with a 14.2248(11), b 9.1670(5), c 59.834(5) Å, ? 90.380(9)°; Z = 8 (2 mols./Z), dc = 2.290; R = 0.041, Rw(F2) = 0.107 for 4743 reflections. The mol. structure is very similar to that of the known dimethylpyrazole deriv. [Ru3(?-H){?-N2C3HMe2-3,5}(CO)10]. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    New iso and heteropolyoxomolybdates: synthesis and molecular structure of the anions [(Mo8O26)-O-VI(OH)](5-), [(HAsAsMoMo8O34)-As-III-Mo-V-Mo-V-O-VI](6-) and [(HAsAsMoMo8O34)-As-III-Mo-V-Mo-V-O-VI{Co(C5H5N)(2)(H2O)(3)}](4-)
    (2002)
    Fidalgo, Eva Garcia
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    Neels, Antonia
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    ;
    The hydrothermal reaction of Na2MoO4 with pyridine in water at pH 5 and 130 degreesC gives the octamolybdate anion [Mo-8(VI) O-26(OH)](5-) (1) which crystallises as the pyridinium salt; its molecular structure derives from that of the parent alpha-octamolybdate anion [Mo-8(VI) O-26](4-) by opening two molybdenum-oxygen bond and adding a hydroxo bridge. The same reaction in the presence of NaAsO2 yields the mixed-valence arsenatomolybdate [Has(III)As(V)Mo(V)Mo(8)(VI)O(34)](6-) (2) which is also isolated as the pyridinium salt. Anion 2 has a lacunary structure like an open basket, which derives from the famous alpha-Keggin structure by removing three edge-sharing MoO6 octahedra and by capping a trioxygen face of three remaning MoO6 octahedra with an AsH group. Reaction of 2 with Co2+ leads to the anion [(HAsAsMoMo8VI)-As-III-Mo-V-Mo-V O-34 {Co(C5H5N)(2)(H2O)(3)}](4-) (3) which crystallises as a double pyridinium salt together with anion 2. The structure of 3 derives from that of 2 by attaching a Co(C5H5N)(2)(H2O)(3) fragment to a terminal oxo ligand. Reaction of 2 with hydrogen peroxide produces the fully oxydised alpha-Keggin anion [(AsMo12O40)-Mo-V-O-VI](3-) (4) which was found to crystallise as the tetrabutylammonium salt surprisingly with three independent molecules in the unit cell, two of them showing a remarkable disorder. (C) 2002 Elsevier Science Ltd. All rights reserved.