Pilar García-Orduña

University of Zaragoza, Caesaraugusta, Aragon, Spain

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Publications (35)142.35 Total impact

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    ABSTRACT: The catalytic activity of various Ir-NSiN-type complexes, containing different ancillary ligands and/or modified NSiN-type ligands, as catalyst precursors for CO2-hydrosilylation has been studied. The results from these experiments evidenced that the activity and selectivity of the above mentioned catalytic systems depend on the nature of the ancillary ligands as well as on the reaction parameters (temperature and CO2-pressure). Thus, the best catalytic performance has been achieved at 328 K and 8 bar of CO2 using the complex [Ir(H)(CF3CO2)(NSiN*)(coe)] (NSiN* = fac-bis-(4-methylpyridine-2-yloxy)methylsilyl) as catalysts precursor.
    No preview · Article · Jan 2016 · Catalysis Science & Technology
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    Full-text · Article · Aug 2015 · Acta Crystallographica Section A: Foundations and Advances
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    ABSTRACT: The copper(I) complexes [Cu(X){2,6-diisopropylphenyl–NHC–(CH2)3Si(OiPr)3}] (X=Cl (2 a); I (2 b), NHC=N-heterocyclic carbene) have been synthesized and characterized. Furthermore, the structure of 2 b has been confirmed by X-ray diffraction studies. Complex 2 a has been successfully anchored in MCM-41 to afford 2–MCM-41. The activity of both the homogeneous, 2 a, and heterogeneous, 2–MCM-41, catalysts in acetophenone hydrosilylation with HSiEt3 and [3+2] cycloaddition of benzyl azide and phenylacetylene has been investigated. The heterogeneous catalyst exhibits catalytic activity for the cycloaddition reaction though, unexpectedly, shows no catalytic activity for hydrosilylation.
    No preview · Article · Jul 2015 · ChemCatChem
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    ABSTRACT: The synthesis of unbridged biscarbene iridium(I) [Ir(cod)(MeIm∩Z)2]+ complexes having N- or O-functionalized NHC ligands (∩Z = 2-methoxybenzyl, pyridin-2-ylmethyl, quinolin-8-ylmethyl) is described. The molecular structures of the complexes show an antiparallel disposition of the carbene ligands that minimize the steric repulsions between the bulky substituents. However, the complexes were found to be dynamic in solution, due to the restricted rotation about the C(carbene)-Ir bond that results in two interconverting diasteromers having different dispositions of the functionalized NHC ligands. A rotational barrier of around 80 kJ mol-1 (298 K) has been determined by 2D EXSY NMR spectroscopy. The iridium(III) dihydride complex [IrH2(MeIm∩Z)2]+ (∩Z = pyridin-2-ylmethyl) has been prepared by reaction of the corresponding iridium(I) complex with molecular hydrogen. These complexes efficiently catalyzed the transfer hydrogenation of cyclohexanone using 2-propanol as a hydrogen source and KOH as base at 80 °C with average TOF values of 117-155 h-1 at 0.1 mol % iridium catalyst loading. All of the catalyst precursors showed comparable activity independent of both the wingtip type at the NHC ligands and the counterion. Mechanistic studies support the involvement of diene free bis-NHC iridium(I) intermediates in these catalytic systems. DFT calculations have shown that a MPV-like concerted mechanism (Meerwein-Ponndorf-Verley mechanism), involving the direct hydrogen transfer at the coordination sphere of the iridium center, might compete with the well-established hydrido mechanism. Indirect evidence of a MPV-like mechanism has been found for the catalyst precursor having NHC ligands having with a pyridin-2-ylmethyl wingtip.
    No preview · Article · Mar 2015 · Organometallics
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    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.
    No preview · Article · Sep 2014 · Dalton Transactions
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    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.
    No preview · Article · Aug 2014 · Organometallics
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    ABSTRACT: The aqua complex (S-Ir,R-C)-[(eta(5)-C5Me5)Ir(Prophos)(H2O)][SbF6](2) [Prophos = (R)-propane-1,2-diyl-bis(diphenylphosphane)] is an active precursor for the asymmetric Diels-Alder reaction of acyclic enals with cyclopentadiene, 2,3-dimethylbutadiene and isoprene. Enantioselectivities up to 78% ee are achieved. The intermediate Lewis acid-dienophile complex (S-Ir,R-C)-[(eta(5)-C5Me5)Ir(Prophos)(ethyl acrolein)][SbF6](2) has been isolated and completely characterized, including the X-ray crystal structure determination. Structural parameters indicate that the disposition of the coordinated dienophile is controlled by CH/pi attractive interactions established between a phenyl group of the Prophos ligand and the aldehyde proton of the coordinated enal. Proton NMR data indicate that these interactions are maintained in solution. From diffractometric and spectroscopic data, the origin of the enantioselectivity is discussed.
    No preview · Article · Apr 2014 · Journal of Molecular Catalysis A Chemical
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    ABSTRACT: The phosphane-hydroxyl ligand (S-C1,R-C2)-Ph2PC(Ph)HC(OH)HCH2OMe (POH) displays kappa P-1, kappa P-2,O, kappa P-3,O,O', and anionic deprotonated kappa P-3,O,O' coordination modes toward the metallic (eta(6)-p-MeC(6)H(4)iPr)Ru moiety. The hydroxyl group in [(eta(6)-p-MeC(6)H(4)iPr)Ru(kappa P-3,O,O'-POH)][SbF6](2) (3) has strong acidic properties. This complex catalyzes the Die Is Alder reaction between cyclopentadiene and trans-beta-nitrostyrene or. methacrolein as well as the Friedel Crafts reaction between indole and methyl 3,3,3,-trifluoropyruvate or trans-beta-nitrostyrene. Solution studies strongly indicate that complex 3 acts as a metallic Lewis acid assisted Bronsted-acid catalyst.
    No preview · Article · Feb 2014 · Organometallics
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    ABSTRACT: The half-sandwich aqua complex (S-Rh,R-C)-[(eta(5)-C5Me5)Rh{(R)-Prophos}(H2O)][SbF6](2) (Prophos = propane-1,2-diylbis(diphenylphosphane)) efficiently catalyzes the asymmetric reaction between N-methyl-2-methylindole and trans-beta-nitrostyrenes (up to 94% ee). The metal-nitroalkene complex involved has been characterized by X-ray crystallography, and the aci-nitro intermediate complex has been spectroscopically detected. A plausible catalytic cycle is proposed.
    No preview · Article · Jan 2014 · Organometallics
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    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.
    Full-text · Article · Jan 2014 · Inorganic Chemistry
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    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.
    Full-text · Article · Nov 2013 · Dalton Transactions
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    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.
    No preview · Article · Jul 2013 · Dalton Transactions
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    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 CH2Cl2 or CHCl3, giving the diiridium(II) products [(Cl)(cod)Ir(μ-NH2)2Ir(cod)(R)] (R=CH2Cl or CHCl2) as a result of a two-center oxidative addition and concomitant metal-metal bond formation. However, reaction with ClCH2CH2Cl 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, PMe2Ph) without splitting of the amido bridges, allowing the detection of mixed COD/phosphane dinuclear complexes [(cod)Rh(μ-NH2)2Rh(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 Cs2CO3, finding that the iridium complex 2 is more active than the rhodium analogue 1.
    Full-text · Article · Apr 2013 · Chemistry - A European Journal
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    ABSTRACT: The synthesis and characterization of cationic iridium(III) aqua complexes of the formula [IrH(H2O)(PN*)(PP)][SbF6](2) (PN* = chiral phosphano oxazoline ligand; PP = diphosphane) as well as that of the OPOF2-containing complex [IrH(OPOF2)(PNiPr)(dppp)][SbF6] (10) are reported. The X-ray molecular structures of [IrH(H2O)(PNInd)(dppe)][SbF6](2) (1), [IrH(H2O)(PNInd)(dppen)][SbF6](2) (2), and 10a have been determined. Dichloromethane solutions of these aqua complexes efficiently catalyze the enantioselective 1,3-dipolar cycloaddition of the nitrone N-benzylidenephenylamine N-oxide to methacrolein and Diels-Alder reactions between cyclopentadiene and trans-beta-nitrostyrenes. In the first case, the catalytic reaction occurs with excellent endo selectivity and ee up to 85%; the Diels Alder reaction occurs rapidly at room temperature with good endo:exo selectivity and ee up to 90%. The dipolar cycloaddition intermediates [IrH(methacrolein)(PNInd)(PP)][SbF6](2) (PP = (S,S)-chiraphos (11), (R)-prophos (12)) have been characterized, and the molecular structure of 11 has been determined by an X-ray structural analysis.
    No preview · Article · Mar 2013 · Organometallics
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    ABSTRACT: Reaction of the dimer [Ir(mu-Cl)(eta(2)-coe)(2)](2) (coe = cyclooctene) with chiral phosphano oxazoline ligands (PN*) renders neutral mononuclear iridium(I) complexes of the formula [IrCl(eta(2)-coe)(PN*)] (1, 2), which in turn are oxidized to the corresponding iridium(III) hydride species [IrCl2H(eta(2)-coe)(PN*)] (3, 4) by treatment with aqueous HCl. The latter react with diphosphanes (PP) in the presence of NaSbF6 to afford cationic complexes of stoichiometry [IrClH(PN*)(PP)][SbF6] (5-16). The fluorophenyldiphosphane-containing compounds [IrClH(PN*)(dfpPe)][SbF6] (15, 16) evolve to the corresponding Ir(I) species [Ir(PN*)(dfppe)][SbF6] (17, 18) by HCl loss. The new compounds have been fully characterized by analytical and spectroscopic means, including the molecular structure determination of [IrCl2H (eta(2)-coe) (PNInd)] (3), [IrClH(PNInd)(dppen)] [SbF6] (6a,b), [IrClH(PNInd)(dppp)] [SbF6] (7a), [IrClH (PNiPr)-(dppP)][SbF6] (13a), [IrClH(pNInd)(dfppe)][SbF6] (is), [Ir(PNInd)(dfppe)][SbF6] (17), and [Ir(PNiPr)(dfpPe)] [SbF6] (18) by X-ray diffractometric methods.
    No preview · Article · Mar 2013 · Organometallics
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    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.
    No preview · Article · Oct 2012 · Journal of Organometallic Chemistry
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    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.
    Full-text · Article · Aug 2012 · Angewandte Chemie International Edition
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    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.
    No preview · Article · Jul 2012 · Dalton Transactions
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    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.
    No preview · Article · Jun 2012 · Organometallics
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    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.
    Full-text · Article · Apr 2012 · Journal of Organometallic Chemistry