The Chemistry of Osmium Clusters with Unsaturated Ligands PDF Download
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Author: James Neville Martin
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Languages : en
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Author: James Neville Martin
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Languages : en
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Author: Chen Hong
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Languages : en
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Author: 王淑儀
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ISBN: 9781374787308
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Languages : en
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Author: Fai Lung Ting
Publisher:
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Category : Ligands
Languages : en
Pages : 432
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Author: Duward F. Shriver
Publisher: Wiley-VCH
ISBN:
Category : Science
Languages : en
Pages : 456
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Seven chapters summarize the current status of organometallic cluster chemistry from the viewpoints of synthesis, structure and bonding, ligand substitution reactions, ligand transformations, polyhedral rearrangement, cluster fragmentation reactions, and metal clusters as homogeneous catalysts. An eighth provides an extensive bibliography of reviews for the period from 1965 to 1988. Annotation copyrighted by Book News, Inc., Portland, OR
Author: Rajesh Khattar
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Languages : en
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Author: Michael W. Day
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Languages : en
Pages : 496
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Author: R. J. Gouldsmit
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Languages : en
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Author: Po-Kwan Jasmine Lau
Publisher: Open Dissertation Press
ISBN: 9781361426869
Category :
Languages : en
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This dissertation, "The Chemistry of Mixed-metal Clusters of Osmium and Rhodium" by Po-kwan, Jasmine, Lau, 劉寶君, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled THE CHEMISTRY OF MIXED-METAL CLUSTERS OF OSMIUM AND RHODIUM Submitted by LAU PO KWAN JASMINE for the degree of Doctor of Philosophy at The University of Hong Kong in December 2005 The general background of metal clusters, the chemistry of osmium-rhodium mixed-metal clusters, and their potential catalytic applications are reviewed. The work in the synthesis, characterizations, and reactivity studies of different series of osmium-rhodium mixed-metal clusters help us to understand the properties and reactivities of new clusters as compared to the bulk metal surface. 1 1 1 A novel face-capping mode of toluene was observed in [Os Rh (μ -η η η - 3 4 3 C H CH )(CO) ] 1. Cluster 1, together with [Os Rh(-H)(η -C H CH )(CO) ] 2 6 5 3 13 4 6 5 3 12 and a known compound [Os Rh (η -C H CH )(-CO)(CO) ], were obtained from 5 2 6 5 3 16 the reaction of [Os Rh(μ-H) (CO) ] with toluene in the presence of an excess 3 3 12amount of 4-vinylphenol. The reaction of [Os Rh(-H) (CO) ] with an excess 3 3 12 amount of 4-vinylphenol (as a hydride acceptor) in refluxing m-xylene, chlorobenzene, or benzene yielded three new clusters [Os Rh {η -C H (CH ) } 5 2 6 4 3 2 6 6 (-CO)(CO) ] 3, [Os Rh (η -C H Cl)(-CO)(CO) ] 4, and [Os Rh (η -C H ) 16 5 2 6 5 16 5 2 6 6 (-CO)(CO) ] 5, respectively. 16 The hydrogenation of [Os Rh (η -C H CH )(-CO)(CO)] with 5 2 6 5 3 16 [Os (-H) (CO) ] resulted in moderate yields of two hydrogen-rich compounds: 3 2 10 [Os Rh (-H) (CO) ] 6 and [Os Rh Cl(-H) (CO) ] 7. The reaction of 7 3 11 23 5 3 8 18 [Os Rh (η -C H CH )(-CO)(CO) ] with hydrogen yielded a new cluster 5 2 6 5 3 16 compound, [Os Rh(-H) (CO) ] 8. A deuterium exchange experiment was 5 5 18 performed on 6, and 7. Both the compounds proved to be able to exchange the H atom with D in the presence of D SO, and the absence of the hydride signal in the 2 4 H NMR spectrum is consistent with this. Therefore, clusters 6 and 7 may serve as appropriate new hydrogen storage models. A detailed discussion of the chemistry of anionic osmium-rhodium mixed-metal clusters with Au cationic fragments using [Au(PPh )Cl] and [(AuCl) L-L], where L 3 2 = dppe (bis(diphenylphosphino)ethane) or dppp (bis(diphenylphosphino)propane), is presented. Two mono-anionic osmium-rhodium mixed-metal clusters [PPN][Os Rh(μ-CO)(CO) ] 9 and [PPN][Os Rh (μ-CO) (CO) ] 10 were prepared 6 19 9 3 2 26 by the thermolysis of [Os Rh(μ-H) (CO) ]. Electrochemistry studies on 10 showed 3 3 12 four successive redox couples, and revealed a novel electron reservoir property. Treatment of 9 with two equivalent of [Au(PPh)Cl] gave compounds [Os Rh Au(CO) (PPh )] 11, and [Os Au (CO) (PPh ) ][Os Rh(μ-CO)(CO) ] 12. 4 3 18 3 5 3 15 3 3 6 19 Both compounds successfully demonstrated the introduction of the Au(PR ) units 3into transition-metal clusters. Two linked clusters [{Os RhAu(μ-CO)(CO) } (dppp)] 6 19 2 13 and [{Os RhAu(μ-CO)(CO) } (dppe)] 14 were prepared by the reaction of 9 6 19 2 with two equivalent [(AuCl) dppp] and [(AuCl) dppe], respectively. 2 2 The synthesis and characterization of linked cluster [{Os (CO) (μ -H)} 3 10 2 2 {μ,μ -NC H C H N}] 15 from the reaction of [Os Rh(μ-H) (CO) ] with aniline in 2 2 6 4 6 4 3 3 12 the presence of an excess amount of 4-vinyl phenol
Author: Kerstin Behrends
Publisher: Springer
ISBN: 9783540936718
Category : Science
Languages : en
Pages : 249
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The present volume, "Organoosmium Compounds" 8 6, systematically covers the litera ture through 1992, including many later references. This volume is the first published of Series 8. This series is devoted to compounds containing two or more osmium atoms. The volume forms a unit with" Organoosmium Compounds" 8 5 (in preparation). 80th volumes deal with trinuclear compounds with ligands other than CO which are bonded to Os by one carbon atom ("1L ligands "), regardless of whether the ligand is additionally coordinated to Os by heteroatoms. Generally CO groups are additional ligands. As is usual in the organometallic Gmelin series, the term "trinuclear" means three osmium atoms in the molecule without regard to any additional metals that may be present. The content and the subdivision of both volumes are described on p. 1. Volume 85 will deal with homometallic compounds in which the bonding C atom of the leading 1L ligand is bonded to Os by one non-bridging Os-C bond. The first part of the present volume, 86, is devoted to homometallic compounds in which the bonding C atom of the 1L ligand bridges two or three Os atoms. A second part deals with all heterometallic compounds with 1L ligands other than CO. An Empirical Formula Index and a Ligand Formula Index for both volumes 8 5 and 86 will be included in volume 8 5. For abbreviations and dimensions used throughout this volume, see p. X.
