Résultat de la recherche
Dinuclear iron, ruthenium and cobalt complexes containing 1,4-dimethyl-1,4,7-triazacyclononane ligands as well as carboxylato and oxo or hydroxo bridges
The reaction of 1,4-dimethyl-1,4,7-triazacyclononane (L–Me2) with FeSO4 • 7H2O in aqueous ethanol gives, in the presence of sodium carboxylates, hydrogen peroxide, sodium hydroxide and KPF6, the dinuclear Fe(III)–Fe(III) complex cations [(L–Me2)2Fe2(O)(OOCR) 2]2+ (R = H: 1, R = CH3: 2, R = C6H5: 3), which crystallise as the hexafluorophosphate salts. The corresponding reaction with RuCl3 • nH2O does not work, however, the analogous Ru(III)–Ru(III) complex [(L–Me2)2Ru2 (O)(OOCCH3)2]2+ (5) can be synthesised by reacting Ru(dmso)4Cl2 with L–Me2, HCl and air in refluxing ethanol, followed by addition of sodium acetate, the mononuclear intermediate (L–Me2)RuCl3 • H2O (4) being also isolated and characterised. The reaction of L–Me2, sodium acetate, hydrogen peroxide and triethylamine with CoCl2 • 6H2O in acetonitrile yields, however, the hydroxo-bridged Co(III)–Co(III) complex [(L–Me2)2Co2 (OH)(OOCCH3)2]3+ (6). The molecular structures of 2, 5 and 6, solved by single-crystal X-ray structure analyses of the hexafluorophosphate salts, reveal for the orange crystals of [2][PF6]2 a Fe–Fe distance of 3.104(1) Å, for the purple crystals of [5][PF6]2 a Ru–Ru distance of 3.230(1) Å, and for the violet crystals of [6][PF6]3 • (CH3)2CO a Co–Co distance of 3.358(1) Å. All six complexes show catalytic activity for the oxidation of isopropanol with hydrogen peroxide in water to give acetone in the presence of ascorbic acid as co-catalyst.
New Ru-3(CO)(12) derivatives with bulky diphosphine ligands: synthesis, structure and catalytic potential for olefin hydroformylation
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.
Conversion of ethylene into ethylidyne on a mixed-metal cluster: synthesis and structure of IrRu4(CO)(15)(mu(4)-CH3)
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.
Reactions of the cationic complex [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(3)](+) with nitrogen-containing heterocycles in aqueous solution
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.
Ru-4(mu-CO)(CO)(9)(eta(4)-mu(4)-C6H4)(eta(2)-mu(1), mu(4)-PPhCH2CH2PPh2): an unusual pyrolysis product of Ru-3(CO)(10)(dppe) containing a benzyne ligand
The thermal decomposition of Ru-3(CO)(10)(dppe) in refluxing benzene gives, in contrast to the pyrolysis of the dppm analogue, the tetranuclear cluster Ru-4(mu-CO)(CO)(9)(eta(4)-mu(4)-C6H4) (eta(2)-mu(1), mu(4)-PCH2CH2PPh2) (1) along with Ru-3 (CO)(9)(eta(2)-mu(1), mu(2)-C6H5)(eta(3)-mu(1), mu(2)-PPhCH2CH2PPb2) (2). The single-crystal structure analysis of 1 reveals a square-planar tetraruthenium skeleton containing a eta(4)-mu(4)-benzyne ligand as well as a eta(2)-mu(1), mu(4)-phosphinidene-phosphine ligand. (C) 2002 Elsevier Science B.V. All rights reserved.
The cluster dication [H6Ru4(C6H6)(4)](2+) revisited: the first cluster complex containing an intact dihydrogen ligand?
A low-temperature H-1-NMR study suggests the tetranuclear cluster dication [H6Ru4(C6H6)(4)](2+) (1) to contain an H-2 ligand that undergoes, upon warming of the solution, an intramolecular exchange with the four hydride ligands at the Ru-4 framework. Whereas two of the three NMR signals at - 120 degrees C in the hydride region show T-1 values in the range 200-300 ms, the least deshielded resonance at delta = - 17.33 ppm exhibits a T-1 value of only 34 ms, characteristic of an H-2 ligand. a re-examination of the single-crystal X-ray structure analysis of the chloride salt of 1 supports this interpretation by a short distance of 1.14(0.15) Angstrom between two hydrogen atoms coordinated as a PI-PI ligand in a side-on fashion to one of the triangular faces of the Ru-4 tetrahedron. The distance between one of the two hydrogen atoms of the H-2 ligand and one of the four hydride ligands is also very short [1.33(0.15) Angstrom], suggesting an additional H-2... H interaction. The presence of this H-3, unit over one of the three Ru-3 faces in 1 may explain the deformation of the Ru-4 skeleton from the expected tetrahedral symmetry. Density functional theory (DFT) calculations on 1 indicate a very soft potential energy surface associated with the respective displacement of the three interacting cofacial hydrogen atoms. In accordance with these results, the cluster dication 1 tends to loose molecular hydrogen to form the cluster dication [H4Ru4(C6H6)(4)](2+) (2). The equilibrium between 1 and 2 can be used for catalytic hydrogenation reactions. (C) 2000 Elsevier Science S.A. All rights reserved.
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)
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.
The cluster dication [(eta(6)-C6H6)(2)(eta(6)-C6Me6)(4)Ru-8(mu(2)-H)(2)(mu(3)-O)(2)(mu(2)-Cl) (2)](2+): a chloro-bridged framework containing two metal tetrahedra
The title complex was obtained by reacting [(eta(6)-C6H6)(eta(6)-C6Me6)(2)Ru-3(mu(2)-H)(3)(mu(3)-O)(+) with RuCl3 . nH(2)O in aqueous solution. it crystallises as the tetrafluoroborate salt. The cationic cluster is formed of two tetrahedral Ru-4 substructures which are held together by two chloro bridges. (C) 2002 Elsevier Science B.V. All rights reserved.
Tri- and tetranuclear mixed-metal clusters containing alkyne ligands: Synthesis and structure of [Ru3Ir(CO)(11)(RCCR ')](-), [Ru2Ir(CO)(9)(RCCR ')](-), and [HRu2Ir(CO)(9)(RCCR ')]
The tetrahedral cluster anion [Ru3Ir(CO)(13)](-) (1) reacts with internal alkynes RC=CR' to afford the alkyne derivatives [Ru3Ir(CO)(11) (RCCR')](-) (2: R = R' = Ph; 3: R = R' = Et; 4: R = Ph; R' = Me; 5: R = R' = Me) which have a butterfly arrangement of the Ru,Ir skeleton in which the alkyne is coordinated in mu(4)-eta(2) fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions [Ru2Ir(CO)(9)(RCCR')](-) (6: R = R' = Ph; 7: R = R' = Et; 8: R = Ph; R' = Me; 9: R = R' = Me), in which the alkyne ligand is coordinated in a mu(3)-eta(2) parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydride clusters [HRu2Ir(Co)(9)(RC=CR')] (10: R = R' = Ph; 11: R = R' = Et; 12: R = Ph; R' = Me; 13: R = R' = Me). The protonation of the butterfly anions 2 and 3, however, gives rise to the formation of the neutral tetrahedral clusters [HRu3Ir(CO)(11)(RCCR')] (14: R = R' = Ph and 15: R = R' = Et), respectively. The analogous clusters [HRu3Ir(CO)(11)(PhCCCH3)] (16) and [HRu3Ir(CO)(11)(CH3CCCH3)] (17) are only accessible from the reaction of the neutral cluster [HRu3Ir(CO)(13)] with the corresponding alkynes. The complexes 2, 4, 5, 6, 10, 12 and 15 are characterised by Xray structure analysis.
Site-selective carbonyl substitution in the mixed-metal cluster anion [H2Ru3Ir(CO)(12)](-): synthesis and characterization of phosphine, phosphite, arsine and stibine derivatives
The reaction of the mixed-metal carbonyl cluster anion [H2Ru3Ir(CO)(12)](-) with PPh3, PMe3, P(OPh)(3), AsPh3 or SbPh3 leads to the mono-substituted derivatives [H2Ru3Ir(CO)(11)L](-) (L = PPh3 1, L = PMe3 2, L = P(OPh)(3) 3, L = AsPh3 4, L = SbPh3 5). Protonation of the anions 1-5 gives the neutral trihydrido derivatives H3Ru3Ir(CO)(11)L (L = PPh3 6, L = PMe3 7, L = P(OPh)(3) 8, L = AsPh3 9, L = SbPh3 10). All new tetranuclear clusters invariably show a tetrahedral arrangement of the Ru3Ir skeleton, as predicted for 60 e systems. The ligand L is coordinated to one of the ruthenium atoms, except in the case of L = PMe3 where two substitution isomers are observed. While the anionic isomers [H2Ru3Ir(CO)(11)(PMe3)](-) (2) could not be separated, the corresponding neutral isomers H3Ru3Ir(CO)(11)(PMe3) (7) could be resolved by thin-layer chromatography. In isomer 7a, the phosphine ligand is coordinated to one of the ruthenium atoms, whereas in isomer 7b the PMe3 ligand is bonded to the iridium atom. The molecular structures of 1, 7b, 8 and 9 were confirmed by a single-crystal X-ray structure analysis. (C) 1999 Elsevier Science S.A. All rights reserved.