Pilar García-Orduña

University of Zaragoza, Caesaraugusta, Aragon, Spain

Are you Pilar García-Orduña?

Claim your profile

Publications (23)98.87 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Complexes of the formula [(η(n)-ring)M(){}][SbF6]2 ((η(n)-ring)M = (η(5)-C5Me5)Rh, (η(5)-C5Me5)Ir, (η(6)-p-MeC6H4iPr)Ru; = hydroxymethylpyridine ligand; {} = (R)-monophos) have been prepared from the corresponding dimers [{(η(n)-ring)MCl}2(μ-Cl)2] through routes involving [(η(5)-C5Me5)RhCl2{}] or [(η(n)-ring)MCl()][SbF6] intermediates. The new complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of [(η(5)-C5Me5)IrCl2{}] (), [(η(6)-p-MeC6H4iPr)RuCl()][SbF6] (), [(η(5)-C5Me5)IrCl{}][SbF6] (), [(η(5)-C5Me5)Rh(){}][SbF6]2 () and [(η(6)-p-MeC6H4iPr)Ru{}{}][SbF6]2 () by X-ray diffractometric methods. From NMR and X-ray data, the absolute configuration of the new chiral compounds was established.
    Dalton Transactions 09/2014; 43(41). DOI:10.1039/c4dt02171a · 4.10 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The coordinated OH group in cationic complexes [{eta(n)-ring)M(NOH)(Solv)][SbF6] and [(eta(n)-ring)M(NOH){(R)-P1}][SbF6](2) ((eta(n)-ring)M = (eta(5)-C5Me5)Rh, (eta(5)-C5Me5)Ir, (eta(6)-p-MeC(6)H(4)iPr)Ru; NOH = hydroxypyridine ligand; (R)-P1 = (R)-monophos) is deprotonated by Na2CO3, rendering bi- or mononuclear compounds of formulas [{(eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)][SbF6](2) and [(eta(n)-ring)M(NO){(R)-P1}][SbF6], respectively. The complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of [((eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)[SbF6](2) (NOH = NOH-1, (eta(n)-ring)M = (eta(5)-C5Me5)Rh, 8a; (eta(6)-p-MeC(6)H(4)iPr)Ru, 8c) and [(eta(5)-C5Me5)Ir(NO)-((R)-P1}][SbF6] (NOH = (R)-NOH-2; (R)-11b) by X-ray diffractometric methods. In complexes [(eta(n)-ring)M(NOH)(P*)1[SbF6](2) (P* = chiral phosphoramidite ligand) the proton of the coordinated hydroxypyridine ligand is able to activate the carbonyl group of methyl 3,3,3-trifluoropyruvate toward the Friedel-Crafts addition of indoles. In most cases, quantitative conversion is achieved in a few minutes, at -70 degrees C, with an ee of up to 8296. NMR data support the activation of the pyruvate by interaction between its carbonyl oxygen and the OH group of the coordinated hydroxymethylpyridine. Therefore, the metallic complexes act as Lewis acid assisted Bronsted acid catalysts.
    Organometallics 08/2014; 33(15):4016-4026. DOI:10.1021/om5005463 · 4.25 Impact Factor
  • Journal of Molecular Catalysis A Chemical 04/2014; 385. DOI:10.1016/j.molcata.2014.01.021 · 3.68 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)](OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane]. The homometallic hexanuclear metallomacrocycles [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 [(1b)2], [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 (M' = Pd [(1c)2], Pt [(1d)2]), and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 (M' = Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature (1)H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 Å × 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.
    Inorganic Chemistry 01/2014; 53(3). DOI:10.1021/ic402838y · 4.79 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Selected secondary phosphanes (H-PR2; R = Ph, Cy, (i)Pr) smoothly react with a parent amido-bridged diiridium cyclooctadiene complex affording mixed amido/(bis)phosphido dinuclear species. A careful investigation of the reaction profile, carried out by experimental and theoretical tools, revealed that, after an initial amido/phosphido exchange, at low temperatures a second molecule of secondary phosphane adds to the dinuclear system through an oxidative addition process leading to a hydrido amido/bis(phosphido) mixed-valence complex [Ir(III)/Ir(I)]. These species rearrange above -10 °C into the most stable isomer that arises from a migration of the hydrido moiety to one of the [double bond, length as m-dash]CH fragments of a coordinated cod molecule, a transformation facilitated by the formation of an intermetallic bond. Further heating of these species reductively eliminates ammonia affording bis(phosphido)-metal-metal bonded complexes.
    Dalton Transactions 11/2013; 43(4). DOI:10.1039/c3dt52911h · 4.10 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Condensation of homochiral primary amines with 1-methyl-1H-imidazole-2-carbaldehyde affords the corresponding imidazolyl-imine compounds () which have been employed as ligands for the preparation of half-sandwich rhodium and iridium complexes of the formula [(η(5)-C5Me5)MCl][SbF6]. Treatment of these chloride compounds with AgSbF6 renders dicationic aqua-complexes [(η(5)-C5Me5)M(H2O)] [SbF6]2 which act as catalysts for the Diels-Alder reaction between methacrolein and cyclopentadiene. Catalysis occurs with good exo : endo selectivity and poor enantioselectivity. All the compounds have been completely characterized by analytical and spectroscopic methods. Characterization includes the molecular structure determination of the complexes [(η(5)-C5Me5)MCl][SbF6] ( = , M = Rh, () Ir (); = , M = Ir ()) and [(η(5)-C5Me5)M(H2O)][SbF6]2 (M = Rh (), Ir ()) using X-ray diffraction. From the stereochemical properties of the organometallic precursors the catalytic outcome is discussed.
    Dalton Transactions 07/2013; 42(32). DOI:10.1039/c3dt51222c · 4.10 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The ready availability of rare parent amido d(8) complexes of the type [{M(μ-NH2 )(cod)}2 ] (M=Rh (1), Ir (2); cod=1,5-cyclooctadiene) through the direct use of gaseous ammonia has allowed the study of their reactivity. Both complexes 1 and 2 exchanged the di-olefines by carbon monoxide to give the dinuclear tetracarbonyl derivatives [{M(μ-NH2 )(CO)2 }2 ] (M=Rh or Ir). The diiridium(I) complex 2 reacted with chloroalkanes such as CH2 Cl2 or CHCl3 , giving the diiridium(II) products [(Cl)(cod)Ir(μ-NH2 )2 Ir(cod)(R)] (R=CH2 Cl or CHCl2 ) as a result of a two-center oxidative addition and concomitant metal-metal bond formation. However, reaction with ClCH2 CH2 Cl afforded the symmetrical adduct [{Ir(μ-NH2 )(Cl)(cod)}2 ] upon release of ethylene. We found that the rhodium complex 1 exchanged the di-olefines stepwise upon addition of selected phosphanes (PPh3 , PMePh2 , PMe2 Ph) without splitting of the amido bridges, allowing the detection of mixed COD/phosphane dinuclear complexes [(cod)Rh(μ-NH2 )2 Rh(PR3 )2 ], and finally the isolation of the respective tetraphosphanes [{Rh(μ-NH2 )(PR3 )2 }2 ]. On the other hand, the iridium complex 2 reacted with PMe2 Ph by splitting the amido bridges and leading to the very rare terminal amido complex [Ir(cod)(NH2 )(PMePh2 )2 ]. This compound was found to be very reactive towards traces of water, giving the more stable terminal hydroxo complex [Ir(cod)(OH)(PMePh2 )2 ]. The heterocyclic carbene IPr (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) also split the amido bridges in complexes 1 and 2, allowing in the case of iridium to characterize in situ the terminal amido complex [Ir(cod)(IPr)(NH2 )]. However, when rhodium was involved, the known hydroxo complex [Rh(cod)(IPr)(OH)] was isolated as final product. On the other hand, we tested complexes 1 and 2 as catalysts in the transfer hydrogenation of acetophenone with iPrOH without the use of any base or in the presence of Cs2 CO3 , finding that the iridium complex 2 is more active than the rhodium analogue 1.
    Chemistry - A European Journal 04/2013; 19(18). DOI:10.1002/chem.201204391 · 5.70 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Diastereomeric mixtures of epimers at metal of the α-amino carboxylate compounds [(ηn-ring)M(Aa)Cl] [(ηn-ring)M = (η5-C5Me5)Rh(III), (η5-C5Me5)Ir(III), (η6-p-MeC6H4iPr)Ru(II); Aa = α-amino carboxylate] can be readily prepared from the corresponding acetylacetonate compounds [(ηn-ring)M(acac)Cl]. In general, even below 0 °C, these complexes epimerise at the metal. The absolute configuration at the metal has been determined by X-ray diffractometric methods and NMR and CD spectroscopies. The molecular structures of the complexes [(η5-C5Me5)M(Aa)Cl] [M(Aa) = Rh(l-Pro), Ir(l-Pro), Rh(MePro), Ir(MePro)] and [(η6-p-MeC6H4iPr)Ru(Aa)Cl] (Aa = Hyp, MePhe, MePro) are reported. Related iodide complexes, [(ηn-ring)M(Aa)I], can be prepared from the corresponding chlorides by halogen metathesis.
    Journal of Organometallic Chemistry 10/2012; 717:152–163. DOI:10.1016/j.jorganchem.2012.07.022 · 2.30 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: From amido to imido: A dinuclear amido-bridged iridium complex promotes the dehydrogenation of alcohols, affording unusual mixed amido/imido Ir(4) and bis(imido) Ir(3) clusters. Theoretical calculations suggest that bridging μ-NH(2) linkages are crucial to achieve the formation of hydrido amine diiridium species, as a result of a concerted net hydrogen transfer through a proposed eight-membered dimetallacycle.
    Angewandte Chemie International Edition 08/2012; 51(33):8259-63. DOI:10.1002/anie.201202936 · 11.34 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The synthesis and characterization of optically active amino carboxylate complexes of formula [(η(6)-arene)Ru(Aa)Cl] (arene = C(6)H(6), C(6)Me(6), Aa = amino carboxylate) as well as those of the related trimers [{(η(6)-arene)Ru(Aa)}(3)][BF(4)](3) are reported. Trimerization takes place with chiral self-recognition: only diastereomers equally configured at the metal, R(Ru)R(Ru)R(Ru) or S(Ru)S(Ru)S(Ru), are detected. The crystal structures of the complexes [(η(6)-C(6)H(6))Ru(Pip)Cl] and [{(η(6)-C(6)Me(6))Ru(Pro)}(3)][BF(4)](3) have been determined by X-ray diffraction methods. Both types of complexes catalyse the hydrogen transfer reaction from 2-propanol to ketones with moderate enantioselectivity (up to 68% ee). The enantiodifferentiation achieved can be accounted for by assuming that Noyori's bifunctional mechanism is operating.
    Dalton Transactions 07/2012; 41(34):10298-308. DOI:10.1039/c2dt30976a · 4.10 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The aqua complexes (SM,RC)-[(η5-C5Me5)M(PROPHOS)(H2O)][SbF6]2 [PROPHOS = (R)-propane-1,2-diylbis(diphenylphosphane); M = Rh (1), Ir (2)] are active catalysts for the asymmetric Diels–Alder reaction between ketones and dienes. At low temperatures, enantioselectivities of up to 89% ee are achieved. The intermediate Lewis acid–dienophile complexes (SM,RC)-[(η5-C5Me5)M(PROPHOS)(MVK)][SbF6]2 (MVK = methyl vinyl ketone; M = Rh (3), Ir (4)) and (SIr,RC)-[(η5-C5Me5)Ir(PROPHOS)(EVK)][SbF6]2 (EVK = ethyl vinyl ketone (5)) have been isolated and characterized by analytical and spectroscopic means, including the determination of the crystal structure of the iridium complexes 4 and 5 by X-ray diffractometric methods. Structural parameters indicate that the dispositions of the coordinated dienophiles are controlled by the CH/π attractive interactions established between a phenyl group of the PROPHOS ligand and the α-vinyl proton of the ketones. Proton NMR parameters indicate that these interactions are maintained in solution. From these data, the stereoselectivity of the catalytic reaction is discussed.
    Organometallics 06/2012; 31(12):4551–4557. DOI:10.1021/om300346s · 4.25 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The reaction between [arachno-6-SB9H12]− and [IrCl(CO)(PMe3)2] affords the previously reported 11-vertex cluster, [8,8,8-(CO)(PMe3)2-arachno-8,7-IrSB9H10] (4), and small amounts of the new 10-vertex iridathiaborane [9,9,9,9-(CO)(H)(PMe3)2-arachno-9,6-IrSB8H10] (5). Alternatively, a rational synthesis of iridathiadecaboranes is effected from the reaction of the 9-vertex anion [arachno-4-SB8H11]− with [MCl(CO)(PPh3)2], to afford new CO-ligated 10-vertex metallathiaboranes of formulation, [9,9,9,9-(CO)(H)(PPh3)2-arachno-9,6-MSB8H10], where M = Rh (6) and Ir (7), in useful yields of 61% and 60% respectively. Treatment of the 11-vertex rhodathiaborane, [8,8-(PPh3)2-8,7-nido-RhSB9H10] (1) with nBuLi, followed by addition of [IrCl(CO)(PMe3)2] affords the 12-vertex iridarhodathiaborane, [1,2-(μ-CO)-1,1,2-(PMe3)3-2-(PPh3)-closo-1,2-IrRhSB9H9] (8) in low yield (0.7%). The 10-vertex metallathiaboranes, 5, 6 and 7, and the bimetallic 12-vertex cluster, 8, have been characterized by multinuclear NMR spectroscopy. In addition, the molecular structures of compounds 5, 6, and 8 have been studied by X-ray diffraction.
    Journal of Organometallic Chemistry 04/2012; s 721–722:23–30. DOI:10.1016/j.jorganchem.2012.04.003 · 2.30 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The versatile synthetic precursor methanolate-bridged title rhodium complex, [Rh(2)(CH(3)O)(2)(C(12)H(6)F(4))(2)] or [Rh(μ-OCH(3))(tfbb)](2) [tfbb = tetrafluorobenzobarrelene or 3,4,5,6-tetrafluorotricyclo[6.2.2.0(2,7)]dodeca-2(7),3,5,9,11-pentaene], has been structurally characterized. The asymmetric unit contains half a molecule that can be expanded via a twofold axis. The title compound has been shown to be a dinuclear rhodium complex where each metal centre is coordinated by two O atoms from two bridging methanolate groups and by the olefinic bonds of a tfbb ligand. Comparison of the bite angles of tfbb, norbornadiene (nbd) and cyclooctadiene (cod) olefins in their η(4)-coordination to rhodium reveals similarities between the tfbb and nbd ligands, which are much more rigid than cod. The short distance found between the distorted square-planar metal centres [2.8351 (4) Å] has been related to the syn conformation of the folded core `RhORhO' ring.
    Acta Crystallographica Section C Crystal Structure Communications 04/2012; 68(Pt 4):m113-6. DOI:10.1107/S0108270112012930 · 0.54 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Two new heteroleptic pentacoordinated Zn(II) complexes (1 and 2) containing 4,4 0 -disubstituted 2,2 0 -bipyridines as the main ligand and curcumin (curc) as an ancillary ligand have been synthesized, spectroscopically and structurally characterized, and tested in vitro towards different human cancer cell lines. While the nitrogen ligands are almost inactive, Zn(II) curc derivatives 1 and 2 show promising and selective anticancer properties. In particular the curc Zn(II) complex 1 shows the strongest growth inhibition in all cell lines, being even more effective than the pure curc in the LAN-5 neuroblastoma cell line. Furthermore, the curc moiety makes the complexes 1 and 2 fluorescent, a feature enabling investigation of their interaction with DNA through a new optical method previously tested with the reference fluorescent intercalator ethidium bromide. This analysis demonstrates that the interaction mode of curc, 1 and 2 with DNA in the double helix favors their alignment perpendicular to the DNA axis, suggesting a partial inter-base intercalation of these Zn(II) complexes.
  • [Show abstract] [Hide abstract]
    ABSTRACT: The [8,8,8-(H)(PPh3)2-9-(Py)-nido-8,7-RhSB9H9] (2)/[1,1-(PPh3)2-3-(Py)-closo-1,2-RhSB9H8] (3) pair catalyzes the hydrogenation of olefins through nido-to-closo transformations. Substitution of the phosphine ligands can lead to an improvement of the catalytic activity of this system. Therefore, the substitutional chemistry of 2 with PMePh2, PMe2Ph, and PMe3 has been studied, leading to the formation of [8,8,8-(H)(PPh3)(PR3)-9-(Py)-nido-8,7-RhSB9H9], where R3 = Me2Ph (5) or Me3 (6), and [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H9], where R3 = MePh2 (4) or Me2Ph (7). Kinetic studies on the reaction of PMe2Ph with 2 indicate that the substitutions follow a dissociative mechanism. The thermal dehydrogenation of 5–7 affords the corresponding closo-derivatives [1,1-(L)(PPh3)-3-(Py)-closo-1,2-RhSB9H8], where L = PMe2Ph (9) or PMe3 (10), and [1,1-(L)2-3-(Py)-closo-1,2-RhSB9H8], where L = PMe2Ph (11) or PMe3 (12). The substitution of PPh3 by the more basic, less bulky phosphines facilitates hydrogen loss and consequent nido-to-closo transformations. The reaction of 5 and 6 with C2H4 promotes a nido-to-closo cluster change and the consequent formation of 10 and 11 together with small amounts of C2H4-ligated [1,1-(η2-C2H4)(L)-3-(Py)-closo-1,2-RhSB9H8], where L = PPh3 (13) or PMe3 (15), characterized in situ by 1H NMR spectroscopy. In the reactions with ethylene, ethane is detected in situ, indicating that the olefin is hydrogenated. The reactions of 5 and 6 with CO afford the CO-ligated [1,1-(CO)(L)-3-(Py)-closo-1,2-RhSB9H8], where L = PMe2Ph (16) or PMe3 (17). The reactivity of the new PR3-ligated nido-clusters versus H2, C2H4, and CO is not improved with the phosphines studied in this work; however, the changes found in the chemical beahavior of this system are dramatic, confirming the tailorability of these 11-vertex rhodathiaboranes and the potential optimization of their catalytic activity by the judicious choice of the exo-polyhedral ligands.
    Organometallics 03/2012; 31(8):2986–2995. DOI:10.1021/om2009205 · 4.25 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The preparation and characterization of optically active half-sandwich osmium(II) complexes with l-α-amino carboxylate ligands (Aa) of formula [(η6-p-MeC6H4iPr)Os(Aa)Cl] are reported. Chloride abstraction renders the corresponding cationic trimers [{(η6-p-MeC6H4iPr)Os(Aa)}3]3+, which were isolated as tetrafluoroborate salts. Trimerization most probably occurs through the chiral-at-metal mononuclear species [(η6-p-MeC6H4iPr)Os(Aa)(MeOH)]+ and takes place with chiral self-recognition: i.e., only the equal configurations at metal ROs,ROs,ROs and SOs,SOs,SOs diastereomers are detected. The molecular structures of the mononuclear complexes [(η6-p-MeC6H4iPr)Os(Aa)Cl] (Aa = MePhe, Pip, MePro) as well as those of the trimers [{(η6-p-MeC6H4iPr)Os(Aa)}3][BF4]3 (Aa = Pro, Pip) are also reported. The metal and, for amino carboxylates with secondary or tertiary amino moieties, also the nitrogen atom are stereogenic centers. Characterization of the new compounds includes determination of their absolute configuration. Assignment of the configurations in solution has been carried out by NOE and circular dichroism experiments. While both configurations are detected for the osmium, the configuration at nitrogen is induced by that of the carbon of the starting l-α-amino acid. Both neutral mononuclear compounds and cationic trimers catalyze the asymmetric transfer hydrogenation from 2-propanol to ketones with up to 82% ee. From stereochemical considerations, the enantiodifferentiation achieved can be accounted for by assuming that Noyori’s bifunctional mechanism is operating.
    Organometallics 03/2012; 31(8):3333–3345. DOI:10.1021/om3001394 · 4.25 Impact Factor
  • Source
    Angewandte Chemie International Edition 12/2011; 50(49):11735-8. DOI:10.1002/anie.201104745 · 11.34 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The aqua complexes [(η6-arene)Ru(prophos)(H2O)][SbF6]2 [prophos = (R)-propane-1,2-diylbis(diphenylphosphane); arene = p-MeC6H4iPr (p-cymene) (1), C6Me6 (2)] are active catalysts for the asymmetric Diels–Alder (DA) reaction of methacrolein and cyclopentadiene. Complexes 1 and 2 and the DA intermediate Lewis acid–dienophile complexes [(η6-arene)Ru(prophos)(methacrolein)][SbF6]2 (arene = p-cymene (3), C6Me6 (4)) have been isolated and characterized by analytical and spectroscopic means, including the X-ray crystal structure determination of compounds 2, 3, and 4. Structural parameters suggest that the disposition of coordinated methacrolein is influenced by the CH/π-attractive interactions established between phenyl groups of the prophos ligand and the CHO proton of the methacrolein. Proton NMR parameters indicate that these interactions are maintained in solution. The role of the apparently innocent η6-arene ligand in the control of the catalytic coordination site is examined from the structural data obtained. From these data, the origin of the enantioselectivity in the DA reaction is discussed.
    Organometallics 12/2011; 30(24):6726–6733. DOI:10.1021/om200944y · 4.25 Impact Factor
  • P. García-Orduña, M. P. Lamata, D. Carmona, F. J. Lahoz
    Acta Crystallographica Section A Foundations of Crystallography 08/2011; 67(a1):C509-C509. DOI:10.1107/S0108767311087113 · 2.07 Impact Factor
  • Pilar García-Orduña, Slimane Dahaoui, Claude Lecomte
    [Show abstract] [Hide abstract]
    ABSTRACT: The crystal structure of the 2:1 charge-transfer complex of tetrathiafulvalene [2,2'-bis(1,3-dithiolylidene)] and bromanil (tetrabromo-1,4-benzoquinone) [(TTF)(2)-BA, (C(6)H(4)S(4))(2)-C(6)Br(4)O(2)] has been determined by X-ray diffraction at room temperature, 100 and 25 K. No structural phase transition occurs in the temperature range studied. The crystal is made of TTF-BA-TTF sandwich trimers. A charge-transfer estimation between donor and acceptor (0.2 e) molecules is proposed in comparison to the molecular geometries of TTF-BA and TTF and BA isolated molecules. Displacement parameters of the molecules have been modeled with the TLS formalism.
    Acta crystallographica. Section B, Structural science 06/2011; 67(Pt 3):244-9. DOI:10.1107/S0108768111015801 · 2.10 Impact Factor

Publication Stats

89 Citations
98.87 Total Impact Points

Institutions

  • 2011–2014
    • University of Zaragoza
      • Department of Inorganic Chemistry
      Caesaraugusta, Aragon, Spain
  • 2012
    • Spanish National Research Council
      • Department of Environmental Chemistry
      Madrid, Madrid, Spain