Voici les éléments 1 - 10 sur 191
  • 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
    ;
    ;
    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
    Application of the novel tandem process Diels-Alder reaction/Ireland-Claisen rearrangement to the synthesis of rac-juvabione and rac-epijuvabione
    (2000-1-12)
    Soldermann, Nicolas
    ;
    Velker, Joerg
    ;
    Vallat, Olivier
    ;
    ;
    The novel tandem process Diels-Alder reaction/Ireland-Claisen rearrangement shows a high diastereoselectivity for the Ireland-Claisen rearrangement starting from the endo-product of the Diels-Alder reaction. Based on this mechanistic knowledge, the novel tandem process could be applied to the synthesis of rac-juvabione.
  • 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
    ;
    ;
    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
    Catalytic Epoxidation of Alkenes by the Manganese Complex of a Reduced Porphyrinogen Macrocycle
    (2012)
    Bruyneel, Frederic
    ;
    Letondor, Christophe
    ;
    Bastuerk, Bjorn
    ;
    Gualandi, Andrea
    ;
    ; ;
    The present paper details the first application of a fully reduced meso-octamethylporphyrinogen macrocycle as an effective ligand for simple operative manganese-catalyzed alkene epoxidn. The efficiency of the novel catalyst was detd. in the presence of various oxidants, apical ligands and acidic/basic additives. Higher reactivity was found in favor of electron-rich alkenes, whereas an electron-deficient conjugated alkene appeared to be a poor substrate in the screening. Sulfur additives were active as apical ligands, whereas nitrogen-contg. additives influenced the reactivity only moderately. Cis-Stilbene and 3?-acetoxy-5-cholestene were epoxidized in a stereoselective manner. The x-ray structures of the new manganese complexes were detd. and showed a rigid planar coordination geometry of the satd. macrocyclic ligand to the metal center. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    The anion [(As5Mo4O20)-Mo-III-O-VI(OCH3)](2-): a new heteropolyoxometalate containing an unusual As5O4 chain
    (2002)
    Laly, Myriam
    ;
    Fidalgo, Eva Garcia
    ;
    ;
    The heteropolyoxometalate [(HAsAsMoMo8O34)-As-III-Mo-V-Mo-V-O-VI](6-) reacts in aqueous solution with an excess of sodium metaarsenite to give a new arsenomolybdate [(As5Mo4O20)-Mo-III-O-VI(OCH3)](2-) which crystallize as the tetrabutylammonium salt. The single-crystal X-ray structure analysis reveals a heteropolyoxometalate anion containing an unusual chain of five arsenic atoms linked to each other by bridging oxygen atoms. (C) 2002 Elsevier Science B.V. 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
    ;
    Neels, Antonia
    ;
    ;
    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
    New diphosphine ligands containing ethylene glycol and amino alcohol spacers for the rhodium-catalyzed carbonylation of methanol
    (2002)
    Thomas, Christophe M.
    ;
    Mafua, Roger
    ;
    ;
    Rusanov, Eduard
    ;
    ;
    The new diphosphine ligands Ph2PC6H4C(O)X(CH2)2OC(O)C6H4PPh2 (X = NH; X = NPh; X = O) and Ph2PC6H4C(O)O(CH2)2O(CH2)2OC (O)C6H4PPh2 (I) as well as the monophosphine ligand Ph2PC6H4C(O)X(CH2)2OH (II) have been prepd. from 2-diphenylphosphinobenzoic acid and the corresponding amino alcs. or diols. Coordination of the diphosphine ligands to rhodium, iridium, and platinum resulted in the formation of the square-planar complexes. In all complexes, the diphosphine ligands are trans coordinated to the metal center, thanks to the large spacer groups, which allow the two phosphorus atoms to occupy opposite positions in the square-planar coordination geometry. The trans coordination is demonstrated unambiguously by the single-crystal X-ray structure anal. of on of these complexes. In the case of the diphosphine ligand I, the spacer group is so large that dinuclear complexes with ligand I in bridging positions are formed, maintaining the trans coordination of the P atoms on each metal center, as shown by the crystal structure anal. of another complex. The monophosphine ligand II reacts with [{Ir(cod)Cl}2] (III) (cod = cyclooctadiene) to give the simple deriv. [Ir(cod)Cl] which is converted into the carbonyl complex [Ir(CO)2Cl] with carbon monoxide. The crystal structure anal. of III also reveals a square-planar coordination geometry in which the phosphine ligand occupies a position cis with respect to the chloro ligand. Some of these diphosphine ligands have been tested as cocatalysts in combination with the catalyst precursors [{Rh(CO)2Cl}2] and [{Ir(cod)Cl}2] or [H2IrCl6] for the carbonylation of methanol at 170°C and 22 bar CO. The best results (TON 800 after 15 min) are obtained for the combination X = NPh/[{Rh(CO)2Cl}2]. After the catalytic reaction, one complex is identified in the reaction mixt. and can be isolated; it is active for further runs without loss of catalytic activity. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Diastereoselective synthesis of (1S,2S,3R,6S) 3-chloro-3-methyl-6-isopropenyl-1,2-cyclohexanediol via Prins reaction induced by zinc and trimethylsilyl chloride
    While attempting to synthesize a potential inhibitor of the biosynthetic step of formation of PEG, a novel catalytic system inducing the Prins reaction was discovered. Treatment of epoxy geranial with Zn and trimethylsilyl chloride gave (1S,2S,3R,6S) 3-Chloro-3-methyl-6-isopropenyl-1,2-cyclohexanediol in high diastereoselcctivity.