1996~2005

22. [60]Fullerene as a Versatile Four-Electron Donor Ligand

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author H. Song, K. Lee, M.-G. Choi, and J. T. Park
journal Organometallics, 2002, 21, 1756
link http://pubs.acs.org/doi/abs/10.1021/om020038f
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A new 1,2-σ-type C60 compound, Os3(CO)7(CNR)(μ3-CNR)(PPh3)(μ3112-C60) (2; R = CH2Ph), is formed from Os3(CO)8(CNR)(μ3-CNR)(μ3121-C60) (1) upon substitution of CO with PPh3 on a triosmium cluster framework. Compounds 1 and 2 are reversibly interconvertible. Further reaction of 2 with PPh3 results in a π-type C60 complex, Os3(CO)6(CNR)(μ3-CNCH2C6H4)(PPh3)(μ-PPh2)(μ-η22-C60) (3), with an Os−Os bond cleavage.

  1. 39. Room-temperature semiconductor gas sensor based on nonstoichoimetric tungsten oxide nanorod film

    Y. S. Kim, S.-C. Ha, K. Kim, H. Yang, S.-Y. Choi, Y. T. Kim, J. T. Park, C. H. Lee, J. Choi, J. Paek, and K. Lee
    Appl. Phys. Lett., 2005, 86, 213105
    Porous tungsten oxide films were deposited onto a sensor substrate with a Si bulk-micromachined hotplate, by drop-coating isopropyl alcohol solution of highly crystalline tungsten oxide (WO2.72)nanorods with average 75nm length and 4nm diam...
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  2. 38. Unusually high performance photovoltaic cell based on a [60]fullerene metal cluster-porphyrin dyad SAM on an ITO electrode

    Y.-J. Cho, T. K. Ahn, C. Y. Lee, K. S. Kim, H. Song, W. S. Seo, K. Lee, S. K. Kim, D. Kim, J. T. Park
    J. Am. Chem. Soc., 2005, 127, 2380
    A self-assembled monolayer (SAM) of a C60−triosmium cluster complex Os3(CO)7(CNR)(CNR‘)(μ3-η2:η2:η2-C60) (ZnP−C60; R = (CH2)3Si(OEt)3, R‘ = ZnP) on an ITO surface exhibits ideal electrochemical responses as well as remarkable enhancement...
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  3. 37. Ortho-Phosphorylation of PPh3 and C60-Assisted Ortho-Metallation of a Diphosphine on a Tetrairidium Cluster Framework

    B. K. Park, M. A. Miah, H. Kang, K. Lee, Y.-J. Cho, D. G. Churchill, S. Park, M.-G. Choi, J. T. Park
    Organometallics, 2005, 24, 675
    A brief thermolysis of the bis-phosphine-substituted tetrairidium cluster Ir4(CO)10(PPh3)2 (1) in chlorobenzene (CB) converts it rapidly to the diphosphine cluster Ir4(CO)7(μ-CO)3{κ2-Ph2P(o-C6H4)PPh2} (2) in 53% yield, providing evidence...
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    36. Preparation of Anatase TiO2 Thin Films with (OiPr)2Ti(CH3COCHCONEt2)2 Precursor by MOCVD

    B.-J. Bae, K. Lee, W. S. Seo, M. A. Miah, and J. T. Park
    Bull. Korean Chem. Soc., 2004, 25, 1661
    The reaction of titanium tetraisopropoxide with 2 equiv of N,N-diethyl acetoacetamide affords Ti(OiPr)2(CH3COCHCONEt2)2 (1) as colorless crystals in 80% yield. Compound 1 is characterized by spectroscopic (Mass and 1H/13C NMR) and microanaly...
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  5. 35. Strong Interfullerene Electronic Communication in a Bisfullerene-Hexarhodium Sandwich Complex

    K. Lee, Y. J. Choi, Y.-J. Cho, C. Y. Lee, H. Song, C. H. Lee, Y. S. Lee, and J. T. Park
    J. Am. Chem. Soc., 2004, 126, 9837
    Reaction of Rh6(CO)12(dppm)2 (dppm = 1,2-bis(diphenylphosphino)methane) with 1.4 equiv. of C60 in chlorobenzene at 120 °C affords a face-capping C60 derivative Rh6(CO)9(dppm)2(μ3-η2,η2,η2-C60) (1) in 73% yield. Treatment of 1 with excess...
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    34. Synthesis of Os3(CO)9(m3-h2:h2:h2-C60) and Os3(CO)8(PPh3)(m3-h2:h2:h2-C60)

    C. Y. Lee, H. Song, K. Lee, and J. T. Park
    Inorg. Synth., 2004, 34, 225
    .
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  7. 33. Novel [60]Fullerene-assisted Ortho-phosphorylation on a Tetrairidium Butterfly Framework

    B. K. Park, M. A. Miah, G. Lee, Y.-J. Cho, K. Lee, S. Park, M.-G. Choi, and J. T. Park
    Angew. Chem. Int. Ed., 2004, 43, 1712
    A mono- to di- and triphosphane transformation occurs on treatment of [Ir4(CO)9(PPh3)3] (1) with C60 to successively afford 2 and 3. The noninnocent, multifunctional C60 ligand plays a crucial role in transforming three PPh3 ligands into...
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  8. 32. Size-dependent Magnetic Properties of Colloidal Mn3O4 and MnO Nanoparticles

    W. S. Seo, H. H. Jo, K. Lee, S. J. Oh, and J. T. Park
    Angew. Chem., Int. Ed., 2004, 43, 1115
    Highly crystalline and monodisperse MnO and Mn3O4 nanoparticles are prepared by thermal decomposition of [Mn(acac)2] in oleylamine under an inert atmosphere in the presence and absence of a small amount of water, respectively (see pictur...
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  9. 31. Two Metal Centers Bridging Two C60 Cages as a Wide Passage for Efficient Interfullerene Electronic Interaction

    G. Lee, Y.-J. Cho, B. K. Park, K. Lee, and J. T. Park
    J. Am. Chem. Soc., 2003, 125, 13920
    The reaction of Ir4(CO)8(PMe3)4 with excess C60 in refluxing 1,2-dichlorobenzene, followed by treatment by CNR (R = CH2C6H5) at 70 °C, affords a fullerene−metal sandwich complex Ir4(CO)3(μ4-CH)(PMe3)2(μ-PMe2)(CNR)(μ-η2,η2-C60)(μ4-η1,η1...
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  10. 30. Osmium Replica of Mesoporous Silicate MCM-48: Efficient and Recyclable Catalyst for Oxidative Cleavage and Dihydroxylation Reactions

    K. Lee, Y.-H. Kim, S. B. Han, H. Kang, S. Park, W. S. Seo, J. T. Park, B. Kim, and S. Chang
    J. Am. Chem. Soc., 2003, 125, 6844
    A three-dimensional networked osmium nanomaterial (N-Os) was prepared by a thermal decomposition of Os3(CO)12 within mesopores of MCM-48. The novel N-Os species shows high catalytic activity and excellent reusability in the oxidat...
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  11. 29. Preparation and Optical Properties of Highly Crystalline, Colloidal, and Size-controlled Indium Oxide Nanoparticles

    W.S. Seo, H. H. Jo, K. Lee, and J. T. Park
    Adv. Mater., 2003, 15, 795
    Highly crystalline and monodisperse In2O3 nanoparticles have been prepared by thermal decomposition of In(acac)3 in oleylamine under inert atmosphere. The particle size of In2O3 can be easily manipulated by changing the experimental cond...
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  12. 28. Synthesis and Optical Properties of Colloidal Tungsten Oxide Nanorods

    K. Lee, W.S. Seo, and J. T. Park
    J. Am. Chem. Soc., 2003, 125, 3408 (Highlighted as "Making Photoluminescent Tungsten Oxide Nanorods," Heart Cut in Chemical Innovation (www.chemistry.org) by American Chemical Society)
    Thermal decomposition of W(CO)6 in oleylamine in the presence of mild oxidant Me3NO·2H2O produces tungsten oxide nanorods with diameters ranging from 3 to 6 nm. The size of nanorods can be easily varied by the employed surfactant ratio...
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    27. [60]Fullerene-Metal Cluster Complexes: Novel Bonding Modes and Electronic Communication

    K. Lee, H. Song, and J. T. Park
    Acc. Chem. Res., 2003, 36, 78
    [60]Fullerene can bind a variety of metal clusters via η2-C60, μ-η2:η2-C60, and μ3-η2:η2:η2-C60 π-type bonding modes. Multiple C60 additions to a single cluster core have also been demonstrated. Modification of the coordination sphere of clu...
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  14. 26. The first observation of four-electron reduction in [60]fullerene-metal cluster self-assembled monolayers (SAMs)

    Y.-J. Cho, H. Song, K. Lee, K. Kim, J. Kwak, S. Kim, and J. T. Park
    Chem. Commun., 2002, 2966
    Self-assembled monolayers (SAMs) of a μ3-η2∶η2∶η2-C60 triosmium cluster complex Os3(CO)8(CN(CH2)3Si(OEt)3)(μ3-η2∶η2∶η2-C60) (2) on ITO or Au surface exhibit ideal, well-defined electrochemical responses and remarkable electrochemical sta...
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  15. 25. Substitution Reaction of a m3-h1:h2:h1-C60 triosmium Cluster Complex and Formation of a Novel m3-h1:h1:h2-C60 Bonding Mode

    H. Song, J.-I. Choi, K. Lee, M.-G. Choi, and J. T. Park
    Organometallics, 2002, 21, 5221
    Decarbonylation of Os3(CO)8(CNR)(μ3-CNR)(μ3-η1:η2:η1-C60) (1; R = CH2Ph) with Me3NO/MeCN and subsequent thermal reactions with various 2e-donor ligands afford the respective substitution products Os3(CO)7(CNR)(μ3-CNR)(L)(C60) (L = (μ-H)2...
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  16. 24. Electrochemistry of Carbidopenta-ruthenium Complexes of C60 and Related Clusters

    A. J. Babcock, J. Li, K. Lee, and J. R. Shapley
    Organometallics, 2002, 21, 3940
    The electrochemical behavior of the face-coordinated C60-carbidopentaruthenium cluster complexes Ru5C(CO)11(PPh3)(μ3-η2,η2,η2-C60) (1), Ru5C(CO)10(μ-η1,η1-dppf)(μ3-η2,η2,η2-C60) (2) (dppf = 1,1‘-bis(diphenylphosphino)ferrocene), and PtRu...
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  17. 23. Ligand-Induced Conversion of p to s C60-Metal Cluster Complexes: Full Characterization of the m3-h1,h2,h1-C60 Bonding Mode

    H. Song, C. H. Lee, K. Lee, and J. T. Park
    Organometallics, 21, 2514-2520
    The reaction of Os3(CO)9(μ3-η2:η2:η2-C60) (1) with PhCH2NPPh3 in chlorobenzene affords the benzyl isocyanide substituted product Os3(CO)8(CNR)(μ3-η2:η2:η2-C60) (2a, R = CH2Ph) in 76% yield. Photolysis of 1 in the presence of an excess of...
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  18. 22. [60]Fullerene as a Versatile Four-Electron Donor Ligand

    H. Song, K. Lee, M.-G. Choi, and J. T. Park
    Organometallics, 2002, 21, 1756
    A new 1,2-σ-type C60 compound, Os3(CO)7(CNR)(μ3-CNR)(PPh3)(μ3-η1:η1:η2-C60) (2; R = CH2Ph), is formed from Os3(CO)8(CNR)(μ3-CNR)(μ3-η1:η2:η1-C60) (1) upon substitution of CO with PPh3 on a triosmium cluster framework. Compounds 1 and 2 a...
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  19. 21. The First Fullerene-Metal Sandwich Complex: An Unusually strong Electronic Communication between Two C60 Cages

    K. Lee, H. Song, B. Kim, J. T. Park, S. Park, and M.-G. Choi
    J. Am. Chem. Soc., 2002, 124, 2872 (Highlighted as "Fullerene-Metal Sandwich," Science Concentrates in C&EN 80, 38)
    Reaction of Rh6(CO)9(dppm)2(μ3-η2,η2,η2-C60) (1) with C60 in refluxing chlorobenzene followed by treatment with CNR (R = CH2C6H5) at room temperature affords the first fullerene−metal sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3-η2,η2,η2-C60)...
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  20. 20. Reversible Interconversion between m,h2,h2- and m3,h2,h2,h2-C60 on a Carbido Pentaosmium Cluster Framework

    K. Lee, Z.-H Choi, Y.-J. Cho, H. Song, and J. T. Park
    Organometallics, 2001, 20, 5564
    Decarbonylation of Os5(CO)14(PPh3) by 2 equiv of Me3NO/CH3CN at room temperature followed by reaction with C60 in refluxing chlorobenzene produces Os5C(CO)11(PPh3)(μ3,η2:η2:η2-C60) (1) in 44% yield. Thermal treatment of 1 at 80 °C under ...
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  21. 19. Synthesis and Characterization of m3-h2,h2,h2-C60 trirhenium Hydrido Cluster Complexes

    H. Song, Y. Lee, Z.-H. Choi, K. Lee, J. T. Park, J. Kwak, and M.-G. Choi
    Organometallics, 2001, 20, 3139
    The reaction of C60 with Re3(μ-H)3(CO)11(NCMe) in refluxing chlorobenzene produces Re3(μ-H)3(CO)9(μ3-η2,η2,η2-C60) (1) in 50% yield. Initial decarbonylation of 1 with Me3NO/MeCN followed by reaction with PPh3 in boiling chlorobenzene aff...
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  22. 18. First Example of the μ3-η1,η2,η1-C60 Bonding Mode: Ligand-Induced Conversion of π to σ C60–Metal Complexes

    H. Song, K. Lee, C. H. Lee, J. T. Park, H. Y. Chang, and M. G. Choi
    Angew. Chem. Int. Ed., 2001, 40, 1500
    A boat-shaped 1,4-cyclohexadiene-like ring is present in the C60 molecule with a novel σ-typeμ3-η1,η2,η1 bonding mode in the clusters 2 a and 2 b. The change in coordination mode was induced by insertion of an RNC ligand into an Os−Os bo...
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  23. 17. Reaction of GaMe3 with H2NCH2CH2NMe2: Synthesis and Characterization of Adducts and Imidogallanes

    J. E. Park, B. J. Bae, K. Lee, J. T. Park, H. Y. Chang, M. G. Choi
    Organometallics, 2000, 19, 5107
    Reaction of GaMe3 with N,N-dimethylethylenediamine (DMEDA) produces adducts, Me3Ga:NH2C2H4NMe2 (1:1, 1) and Me3Ga:NH2C2H4NMe2:GaMe3 (2:1, 2). A fast concerted intermolecular exchange of the two inequivalent GaMe3 moieties occurs in 2 at ...
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    16. Hydrocarbyl Ligand transformation on the Tungsten-triosmium Cluster Framework

    J. T. Park, J. R. Shapley, K. Lee, and H. Song
    J. Cluster. Sci., 2000, 11, 343
    A comprehensive review of the hydrocarbon derivative chemistry of WOs3 mixed-metal cluster compounds including synthesis, reactivity, ligand transformation, and solution dynamics is presented.
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  25. 15. Reversible Interconversion between m3-h2,h2,h2- to m-h2,h2-C60 on a Carbido Pentaosmium Cluster Framework

    K. Lee, C. H. Lee, H. Song, J. T. Park, H. Y. Chang, and M.-G. Choi
    Angew. Chem. Int. Ed., 2000, 39, 1801
    Carbonyl addition or elimination reactions on an Os5C cluster framework result in a novel interconversion between two C60 bonding modes: μ3-η2,η2,η2-C60 for 1 and μ-η2,η2-C60 for 2. The latter bonding mode had been elusive until now, and...
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    14. Fluxional Processes and Structural Characterization of m3-h2,h2,h2-C60 triosmium Cluster Complexes, Os3(CO)9-n(PMe3)n(m3-h2,h2,h2-C60) (n=1,2,3)

    H. Song, K. Lee, J. T. Park, and M.-G. Choi
    J. Organomet. Chem., 2000, 599, 49
    The title complex, Os3(CO)6(PMe3)3(μ3-η2,η2,η2-C60) (3), has been prepared by decarbonylation of Os3(CO)9(μ3-η2,η2,η2-C60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os3(CO)7(PMe3)2(μ...
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    13. trans-cis Isomerization and Structure of Dimeric [Me2M-m-N(H)NPh2]2 (M = Al, Ga)

    D. Cho, J. E. Park, B.-J. Bae, K. Lee, B. Kim, and J. T. Park
    J. Organomet. Chem., 1999, 592, 162
    Reaction of MMe3 (M=Al, Ga) with one equivalent of NH2NPh2 affords a dimeric complex [Me2M-μ-N(H)NPh2]2 [M=Al (1), M=Ga (2)] as a mixture of trans and cis isomers. Purification of 1 and 2 by recrystallization gives only trans isomers 1a and ...
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    12. Synthesis and Characterization of (CH3C(CH2PPh2)3)RhH(h2-C60)

    H. Song, K. Lee, J. T. Park, and I.-H. Suh
    J. Organomet. Chem., 1999, 584, 361
    The title complex, (triphos)RhH(η2-C60) (2) (triphos=CH3C(CH2PPh2)3), was prepared by the reaction (80°C, toluene) of C60 with a trihydride rhodium complex (triphos)RhH3(1) in high yield (86%) as green crystals and characterized by spectrosc...
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  29. 11. Synthesis, Structure, and Electrochemical Studies of m3-h2,h2,h2-C60 triosmium Complexes

    H. Song, K. Lee, J. T. Park, and M.-G. Choi
    Organometallics, 1998, 17, 4477
    Two μ3-η2,η2,η2-C60 complexes, Os3(CO)8(PPh3)(μ3-η2,η2,η2-C60) (8) and Os3(CO)7(PMe3)2(μ3-η2,η2,η2-C60) (9), have been prepared by decarbonylation of Os3(CO)9(μ3-η2,η2,η2-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The...
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  30. 10. Substitution Site Specificity on the Ru10C2 Cluster Framework. Multiple Convergent Pathways to the Mixed Hydrocarbon Ligand Derivative Ru10C2(CO)21(NBD)(C2Ph2)

    K. Lee and J. R. Shapley
    Organometallics, 1998, 17, 4368-4373
    The substitution of carbonyl ligands in the edge-shared bioctahedral cluster [PPN]2[Ru10C2(CO)24] by two types of 4e donor π-bonding ligands, viz., a diene (norbornadiene) and an alkyne (diphenylacetylene), has been investigated under va...
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  31. 9. Reversible transformation between Methylene and Methylidyne-Hydride on the Ru10C2 Framework

    K. Lee, S. R. Wilson, and J. R. Shapley
    Organometallics, 1998, 17, 4113
    Oxidative substitution of [Ru10C2(CO)22(NBD)]2- with ferrocenium/diazomethane forms a methylene derivative, Ru10C2(CO)22(NBD)(CH2), in which the methylene ligand symmetrically bridges two adjacent apical ruthenium centers in the e...
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  32. 8. Substitution of [Ru10C2(CO)24]2- with Allene. Reversible Formation of [Ru10C2(CO)22(C3H4)2- and [Ru10C2(CO)20(C3H4)2]2

    K. Lee and J. R. Shapley
    Organometallics, 1998, 17, 4030
    Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene proceeds cleanly in diglyme at 90 °C (1 atm) to afford the monosubstituted derivative [Ru10C2(CO)22(μ-η2:η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at...
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  33. 7. Face Coordinated C60 Complexes with Carbido Pentaruthenium Cluster Cores including a Bimetallic Platinum-Pentaruthenium Complex

    K. Lee and J. R. Shapley
    Organometallics, 1998, 17, 3020
    Interaction of C60 with Ru5C(CO)15 or PtRu5C(CO)14(COD) in hot chlorobenzene, followed by treatment with solubilizing phosphines, provides compounds with hexahapto coordination of C60 to a Ru3 face of the square pyramidal Ru5C or octahed...
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    6. High Nuclearity Hydridodecaruthenium Clusters

    M. P. Cifuentes, M. G. Humphrey, J. R. Shapley, K. Lee
    Inorg. Synth., 1998, 32, 287
    .
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    5. Tri(μ-carbonyl)Nonacarbonyltetrarhodium, Rh4(μ-CO)3(CO)9

    Ph. Serp, Ph. Kalck, R. Feurer, R. Morancho, K. Lee, J. R. Shapley
    Inorg. Synth., 1998, 32, 284
    .
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    4. Platinum-Ruthenium Carbonyl Cluster Complexes

    R. D. Adams, T. S. Barnard, J. E. Cortopassi, W. Wu, Z. Li, J. R. Shapley, K. Lee
    Inorg. Synth., 1998, 32, 280
    .
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  37. 3. Oxidative Substitution of [Ru10C2(CO)24]2- with Disubstituted Alkynes. Facile Formation and Reduction of Ru10C2(CO)23(C2RR')

    J. W. Benson, T. Ishida, K. Lee, S. R. Wilson, and J. R. Shapley
    Organometallics, 1997, 16, 4929
    Oxidation of the decaruthenium carbonyl cluster [Z]2[Ru10C2(CO)24] (1) (Z+ = PPN+, Et4N+) with [Cp2Fe][BF4] (2 equiv) at room temperature in the presence of disubstituted alkynes forms the neutral derivatives Ru10C2(CO)23(C2RR‘) (2, R, R...
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    2. Coordination of C60 to Penta- and Hexaruthenium Cluster Frames

    K. Lee, H.-F. Hsu, and J. R. Shapley
    Organometallics, 1997, 16, 3876
    In refluxing chlorobenzene C60 reacts with Ru5C(CO)15 or with Ru6C(CO)17 to form new complexes, which are isolated following treatment with tertiary phosphines to give the structurally characterized, facebonded derivatives Ru5C(CO)11(PPh...
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    1. Characterization and structures of intermediates in the reactivity of CpWOs3(CO)11(μ3-CTol) towards dihydrogen and water

    J. T. Park, J.-H. Chung, H. Song, K. Lee, J.-H. Lee, J.-R. Park, and I.-H. Suh
    J. Organomet. Chem., 1996, 526, 215
    Initial decarbonylation of CpWos3(Co)11(μ3-CTol) (1: Cp = η5-C5H5, Tol = p-C6H4Mc) with the Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido comlex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a ‘butterfly’ cluster with a 6...
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