16 Topic in Organometallic Chemistry

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<ul><li><p>16Topics in Organometallic Chemistry</p><p>Editorial Board:</p><p>J.M. Brown P. H. Dixneuf A. Frstner L. S. HegedusP. Hofmann P. Knochel G. van Koten S. Murai M. Reetz</p></li><li><p>Topics in Organometallic ChemistryRecently Published and Forthcoming Volumes</p><p>Surface and Interfacial OrganometallicChemistry and CatalysisVolume Editors: C. Copret, B. ChaudretVol. 16, 2005</p><p>Chiral Diazaligands for Asymmetric SynthesisVolume Editors: M. Lemaire, P. MangeneyVol. 15, 2005</p><p>Palladium in Organic SynthesisVolume Editor: J. TsujiVol. 14, 2005</p><p>Metal Carbenes in Organic SynthesisVolume Editor: K.H. DtzVol. 13, 2004</p><p>Theoretical Aspects of Transition Metal CatalysisVolume Editor: G. FrenkingVol. 12, 2005</p><p>Ruthenium Catalysts and Fine ChemistryVolume Editors: C. Bruneau, P. H. DixneufVol. 11, 2004</p><p>New Aspects of Zirconium Containing OrganicCompoundsVolume Editor: I. MarekVol. 10, 2004</p><p>Precursor Chemistry of Advanced MaterialsCVD, ALD and NanoparticlesVolume Editor: R. FischerVol. 9, 2005</p><p>Metallocenes in Stereoselective SynthesisVolume Editor: T. TakahashiVol. 8, 2004</p><p>Transition Metal Arene -Complexes in OrganicSynthesis and CatalysisVolume Editor: E. P. KndigVol. 7, 2004</p><p>Organometallics in Process ChemistryVolume Editor: R. D. LarsenVol. 6, 2004</p><p>Organolithiums in Enantioselective SynthesisVolume Editor: D.M. HodgsonVol. 5, 2003</p><p>Organometallic Bonding and Reactivity:Fundamental StudiesVolume Editor: J.M. Brown, P. HofmannVol. 4, 1999</p><p>Activation of Unreactive Bonds and OrganicSynthesisVolume Editor: S. MuraiVol. 3, 1999</p><p>Lanthanides: Chemistry and Use in OrganicSynthesisVolume Editor: S. KobayashiVol. 2, 1999</p><p>Alkene Metathesis in Organic SynthesisVolume Editor: A. FrstnerVol. 1, 1998</p></li><li><p>Surface and Interfacial OrganometallicChemistry and Catalysis</p><p>Volume Editors: Christophe Copret Bruno Chaudret</p><p>With contributions by</p><p>J.-M. Basset F. Bonino S. Bordiga R. L. Brutchey J.-P. CandyB. Chaudret C. Copret A. Damin H.-J. Freund K. L. FujdalaB. C. Gates E. Groppo C. Lamberti C. Prestipino T. RisseA. Roucoux T.D. Tilley A. Zecchina</p><p>123</p></li><li><p>The series Topics in Organometallic Chemistry presents critical reviews of the present and future trendsin polymer and biopolymer science including chemistry, physical chemistry, physics and materialscience. It is adressed to all scientists at universities and in industry who wish to keep abreast ofadvances in the topics covered.As a rule, contributions are specially commissioned. The editors and publishers will, however, alwaysbe pleased to receive suggestions and supplementary information. Papers are accepted for Topics inOrganometallic Chemistry in English.In references Topics in Organometallic Chemistry is abbreviated Top Organomet Chem and is cited asa journal.</p><p>Springer WWW home page: http://www.springeronline.comVisit the TOMC content at http://www.springerlink.com/</p><p>Library of Congress Control Number: 2005928333</p><p>ISSN 1436-6002ISBN-10 3-540-26496-5 Springer Berlin Heidelberg New YorkISBN-13 978-3-540-26496-5 Springer Berlin Heidelberg New YorkDOI 10.1007/b105251</p><p>This work is subject to copyright. All rights are reserved, whether the whole or part of the materialis concerned, specically the rights of translation, reprinting, reuse of illustrations, recitation, broad-casting, reproduction on microlm or in any other way, and storage in data banks. Duplication ofthis publication or parts thereof is permitted only under the provisions of the German Copyright Lawof September 9, 1965, in its current version, and permission for use must always be obtained fromSpringer. Violations are liable for prosecution under the German Copyright Law.</p><p>Springer is a part of Springer Science+Business Media</p><p>springeronline.com</p><p>c Springer-Verlag Berlin Heidelberg 2005Printed in Germany</p><p>The use of registered names, trademarks, etc. in this publication does not imply, even in the absenceof a specic statement, that such names are exempt from the relevant protective laws and regulationsand therefore free for general use.</p><p>Cover design: Design &amp; Production GmbH, HeidelbergTypesetting and Production: LE-TEX Jelonek, Schmidt &amp; Vckler GbR, Leipzig</p><p>Printed on acid-free paper 02/3141 YL 5 4 3 2 1 0</p></li><li><p>Volume Editors</p><p>Christophe Copret</p><p>Laboratoire de Chimie Organometalliquede Surface43 Bd du 11 Novembre 191869616 Villeurbanne, Francecoperet@cpe.fr</p><p>Bruno Chaudret</p><p>Laboratoire de Chimie de Coordinationdu CNRSroute de Narbonne31077 Toulouse Cdex 04, Francechaudret@lcc-toulouse.fr</p><p>Editorial Board</p><p>Dr. John M. Brown</p><p>DysonPerrins Laboratory SouthParksRoadOxford OX13QYjohn.brown@chem.ox.ac.uk</p><p>Prof. Alois Frstner</p><p>Max-Planck-Institut fr KohlenforschungKaiser-Wilhelm-Platz 145470 Mhlheim an der Ruhr, Germanyfuerstner@mpi-muelheim.mpg.de</p><p>Prof. Peter Hofmann</p><p>Organisch-Chemisches InstitutUniversitt HeidelbergIm Neuenheimer Feld 27069120 Heidelberg, Germanyph@phindigo.oci.uni-heidelberg.de</p><p>Prof. Gerard van Koten</p><p>Department of Metal-Mediated SynthesisDebye Research InstituteUtrecht UniversityPadualaan 83584 CA Utrecht, The Netherlandsvankoten@xray.chem.ruu.nl</p><p>Prof. Manfred Reetz</p><p>Max-Planck-Institut fr KohlenforschungKaiser-Wilhelm-Platz 145470 Mlheim an der Ruhr, Germanyreetz@mpi.muelheim.mpg.de</p><p>Prof. Pierre H. Dixneuf</p><p>Campus de BeaulieuUniversity de Rennes 1Av. du Gl Leclerc35042 Rennes Cedex, FrancePierre.Dixneuf@univ-rennesl.fr</p><p>Prof. Louis S. Hegedus</p><p>Department of ChemistryColorado State UniversityFort Collins Colorado 80523-1872USAhegedus@lamar. colostate.edu</p><p>Prof. Paul Knochel</p><p>Fachbereich ChemieLudwig-Maximilians-UniversittButenandstr. 5-13Gebude F81377 Mnchen, Germanyknoch@cup.uni-muenchen.de</p><p>Prof. Shinji Murai</p><p>Faculty of EngineeringDepartment of Applied ChemistryOsaka UniversityYamadaoka 2-1, Suita-shi Osaka 565Japanmurai@chem.eng.osaka-u.ac.jp</p></li><li><p>Topics in Organometallic ChemistryAlso Available Electronically</p><p>For all customers who have a standing order to The Handbook of Environmen-tal Chemistry, we offer the electronic version via SpringerLink free of charge.Please contact your librarian who can receive a password or free access to thefull articles by registering at:</p><p>springerlink.com</p><p>If you do not have a subscription, you can still view the tables of contents of thevolumes and the abstract of each article by going to the SpringerLink Home-page, clicking on Browse by Online Libraries, then Chemical Sciences, andnally choose The Handbook of Environmental Chemistry.</p><p>You will nd information about the</p><p> Editorial Board Aims and Scope Instructions for Authors Sample Contribution</p><p>at springeronline.com using the search function.</p></li><li><p>Preface</p><p>Molecular chemistry has laid down the rules for understanding and prepar-ingwell-denedorganometallic andmetallo-organic complexes that havebeencentral to thedevelopment of homogeneous catalysts. Thegoal of this book is toshow that molecular chemistry is also a tool for studying much larger systems,such as those involved in heterogeneous catalysis. Heterogeneous catalysts aretypically made of oxide materials, metallic particles, or organometallic com-ponents. While the main part of the catalyst is constituted by the bulk of thematerial, the catalytic events take place at the interface between the reactantphase and the surface of the material, and more specically at the active sites.Thus, these systems correspond to large ensembles of atoms (metal particlesor oxides), which are composed of organometallic and metallo-organic build-ing blocks, and active sites, which can be described as organometallic andmetallo-organic centres. It is therefore obvious that molecular organometallic(and inorganic) chemistry must play an essential role in the eld of hetero-geneous catalysis whether discussing the method of preparation of catalysts,the understanding of catalytic phenomena on surfaces, or the rational devel-opment of better catalysts. In this book, we have therefore addressed thesevarious questions through selected examples. The rst two chapters focus onthemolecular understanding of known industrial heterogeneous catalysts. Thethird contribution discusses the synthesis and the properties of tailored oxidematerials. The next paper addresses the use of surface science as a tool for un-derstanding the active sites of heterogeneous catalysts. The fth chapter tack-les the preparation of well-dened active sites through surface organometallicchemistry and their relation to the understanding of industrial processes. Thesixth contribution discusses the use of metal clusters as a model of metallicparticles. Finally, the remaining two chapters focus on the use of well-denedorganometallic complexes for the synthesis of nanoparticles and their use incatalysis.</p><p>Villeurbanne, Toulouse, Bruno ChaudretSeptember 2005 and Christophe Copret</p></li><li><p>Contents</p><p>Anatomy of Catalytic Centers in Phillips Ethylene Polymerization CatalystA. Zecchina E. Groppo A. Damin C. Prestipino . . . . . . . . . . . . 1</p><p>Single Site Catalyst for Partial Oxidation Reaction: TS-1 Case StudyS. Bordiga A. Damin F. Bonino C. Lamberti . . . . . . . . . . . . . . 37</p><p>Tailored Oxide Materials via Thermolytic Molecular Precursor (TMP)MethodsK. L. Fujdala R. L. Brutchey T. D. Tilley . . . . . . . . . . . . . . . . . 69</p><p>Spectroscopic Characterization of Organometallic Centers on InsulatorSingle Crystal Surfaces: From Metal Carbonyls to ZieglerNatta CatalystsT. Risse H.-J. Freund . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117</p><p>Analogy between Surface and Molecular Organometallic ChemistryJ.-P. Candy C. Copret J.-M. Basset . . . . . . . . . . . . . . . . . . . 151</p><p>Oxide- and Zeolite-supported Molecular Metal Clusters: Synthesis,Structure, Bonding, and Catalytic PropertiesB. C. Gates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211</p><p>Synthesis and Surface Reactivity of Organometallic NanoparticlesB. Chaudret . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233</p><p>Stabilized Noble Metal Nanoparticles: An Unavoidable Familyof Catalysts for Arene Derivative HydrogenationA. Roucoux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261</p><p>Author Index Volumes 116 . . . . . . . . . . . . . . . . . . . . . . . . 281</p><p>Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289</p></li><li><p>Top Organomet Chem (2005) 16: 135DOI 10.1007/b138072 Springer-Verlag Berlin Heidelberg 2005Published online: 14 September 2005</p><p>Anatomy of Catalytic Centersin Phillips Ethylene Polymerization Catalyst</p><p>A. Zecchina () E. Groppo A. Damin C. Prestipino</p><p>Department of Inorganic, Physical and Materials Chemistry and NIS Centreof Excellence, University of Torino, Via P. Giuria 7, 10125 Torino, Italyadriano.zecchina@unito.it</p><p>1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2</p><p>2 Spectroscopic Characterization of the Catalyst . . . . . . . . . . . . . . . . 42.1 Surface of the Silica Support . . . . . . . . . . . . . . . . . . . . . . . . . . 42.2 Anchoring Process and Structure of Anchored Cr(VI) . . . . . . . . . . . . 72.3 Reduction Process and Structure of Reduced Chromium . . . . . . . . . . 102.3.1 Oxidation State of Reduced Chromium . . . . . . . . . . . . . . . . . . . . 102.3.2 Structure of Cr(II) Sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11</p><p>3 Catalytic Activity and Polymerization Mechanism . . . . . . . . . . . . . . 193.1 Active Sites and Turnover Number . . . . . . . . . . . . . . . . . . . . . . . 203.2 First Spectroscopic Attempts to Determine the Polymerization Mechanism 213.3 Polymerization Mechanisms Proposed in the Literature . . . . . . . . . . . 233.3.1 Ethylene Coordination, Initiation and Propagation Steps . . . . . . . . . . 233.3.2 Standard Cossee Model for Initiation and Propagation . . . . . . . . . . . . 253.3.3 Carbene Model for Initiation and Propagation . . . . . . . . . . . . . . . . 263.3.4 Metallacycles Model for Initiation and Propagation . . . . . . . . . . . . . 263.3.5 Conclusions and Future Improvements . . . . . . . . . . . . . . . . . . . . 28</p><p>4 Open Questions and Perspectives . . . . . . . . . . . . . . . . . . . . . . . 30</p><p>References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32</p><p>Abstract A relevant fraction of the polyethylene produced in the world (about 30%) isobtained with the Phillips process. Many efforts in the last 30 years have been devotedto establish the valence state and the structure of the catalytically active species formedby reduction with ethylene. However, no certain conclusions have been obtained so far,even using a CO-prereduced simplied system. In this review it will be shown that theCO-reduced system, although highly homogeneous from the point of view of the va-lence state (denitely II) and nuclearity, is heterogeneous as far the local structure of thesites is concerned. Only Cr(II) ions with the lowest coordination (which unfortunatelyare only a minor fraction of the total) are responsible for the catalytic activity, whilethe overwhelming majority of surface sites play the role of spectator under normal reac-tion conditions. In the second part of the review the proposed initiation/polymerizationmechanisms are fully reported. A peculiarity of the Cr/SiO2 system, which makes itunique among the polymerization catalysts (ZieglerNatta, metallocenes, etc.), lies in thefact that it does not requires any activator (such as aluminium alkyls etc.) because ethy-lene itself is able to create the catalytic center from the surface chromate precursor. It willbe shown that a unifying picture has not yet been achieved, even in this case. The aim of</p></li><li><p>2 A. Zecchina et al.</p><p>this review is to illustrate, on one side, how much progress has been made recently in theunderstanding of the sites structure and, on the other side, the strategies and the tech-niques which can be adopted to study the catalyst under working conditions. It will beshown that the methods adopted for the Cr/SiO2 system have paradigmatic character andcan be extended to other catalytic systems.</p><p>Keywords Chromium Ethylene polymerization Phillips catalyst</p><p>AbbreviationsCT Charge transferDFT Density functional theoryDRS Diffuse reectance spectroscopyEPR Electron paramagnetic resonanceEXAFS Extended X-ray absorption ne structure spectroscopyFT Fourier transformFTIR Fourier transformed infrared spectroscopyIR Infrared spectroscopyMAO MethylalumoxaneNMR Nuclear magnetic resonancePE PolyethyleneRT Room temperatureSIMS Secondary ions mass spectroscopyTOF Turnover frequencyUV-Vis Ultraviolet-visible spectroscopyXANES X-ray absorption near edge structure spectroscopyXPS X-ray photoelectron spectroscopyOCrO angle O Cr OSiOSi angle Si O SiAB A-B stretching modeAB A-B stretching frequency(CO) variation of the C O stretching frequency with respect to that in the gas phase</p><p>1Introduction</p><p>The discovery of olen polymerization catalysts in the early 1950s by Zieglerand Natta represents a milestone in industrial catalysis. Tremendous evo-lution has taken place since then: today, fourth generation ZieglerNattacatalysts and metallocene-based single-site catalysts display activity andster...</p></li></ul>

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