Silica-supported Ligands and Organometallics PDF Download
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Author: Tom Vancompernolle
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Book Description
The generation of heterogeneous catalysts featuring well-defined active centers is of high importance, considering the expected benefits in terms of efficiency and of understanding. We used the surface organometallic chemistry approach to address this issue, focusing on the grafting of rare-earth metals and aluminum derivatives onto silica, and relying mostly on advanced, high-field solid state NMR for detailed characterization at the molecular level, with an emphasis on quadrupolar nuclei. Thus, the grafting of lanthanum benzyl and rare-earth metal silylamide precursors onto silica was studied, along with applications in several catalytic processes related to polymerization and fine chemistry. The impact from the immobilization is mostly found in selectivity, as supported species behave differently from the molecular counterparts. Furthermore, several aluminum species (salen derivatives, along with alkyl and chloroalkyl complexes) were immobilized onto silica, affording catalysts and cocatalysts for the carbonatation of epoxides and for the polymerization and oligomerization of olefins. There again, strong influence of the grafting was observed on the products resulting from catalysis, for instance shifting from short chain olefins to polyethylene upon use of grafted cocatalysts for oligomerization. Finally, a novel methodology for the introduction of chelating bidentate monoanionic fragments onto silica was introduced and implemented for palladium and iridium species' immobilization. Preliminary catalytic applications were encouraging.
Author: Tom Vancompernolle
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Book Description
The generation of heterogeneous catalysts featuring well-defined active centers is of high importance, considering the expected benefits in terms of efficiency and of understanding. We used the surface organometallic chemistry approach to address this issue, focusing on the grafting of rare-earth metals and aluminum derivatives onto silica, and relying mostly on advanced, high-field solid state NMR for detailed characterization at the molecular level, with an emphasis on quadrupolar nuclei. Thus, the grafting of lanthanum benzyl and rare-earth metal silylamide precursors onto silica was studied, along with applications in several catalytic processes related to polymerization and fine chemistry. The impact from the immobilization is mostly found in selectivity, as supported species behave differently from the molecular counterparts. Furthermore, several aluminum species (salen derivatives, along with alkyl and chloroalkyl complexes) were immobilized onto silica, affording catalysts and cocatalysts for the carbonatation of epoxides and for the polymerization and oligomerization of olefins. There again, strong influence of the grafting was observed on the products resulting from catalysis, for instance shifting from short chain olefins to polyethylene upon use of grafted cocatalysts for oligomerization. Finally, a novel methodology for the introduction of chelating bidentate monoanionic fragments onto silica was introduced and implemented for palladium and iridium species' immobilization. Preliminary catalytic applications were encouraging.
Author: Jean-Marie Basset
Publisher: Springer Science & Business Media
ISBN: 9400929714
Category : Science
Languages : en
Pages : 340
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Book Description
Surface organometallic chemistry is a new field bringing together researchers from organometallic, inorganic, and surface chemistry and catalysis. Topics ranging from reaction mechanisms to catalyst preparation are considered from a molecular basis, according to which the "active site" on a catalyst surface has a supra-molecular character. This. the first book on the subject, is the outcome of a NATO Workshop held in Le Rouret. France, in May. 1986. It is our hope that the following chapters and the concluding summary of recommendations for research may help to provide a definition of surface organometallic chemistry. Besides catalysis. the central theme of the Workshop, four main topics are considered: 1) Reactions of organometallics with surfaces of metal oxides, metals. and zeolites; 2) Molecular models of surfaces, metal oxides, and metals; 3) Molecular approaches to the mechanisms of surface reactions; 4) Synthesis and modification of zeolites and related microporous solids. Most surface organometallic chemistry has been carried out on amorphous high-surf ace-area metal oxides such as silica. alumina. magnesia, and titania. The first chapter. contributed by KNOZINGER. gives a short summary of the structure and reactivity of metal oxide surfaces. Most of our understanding of these surfaces is based on acid base and redox chemistry; this chemistry has developed from X-ray and spectroscopic data, and much has been inferred from the structures and reactivities of adsorbed organic probe molecules. There are major opportunities for extending this understanding by use of well-defined (single crystal) oxide surfaces and organometallic probe molecules.
Author: Mallory Kim Neuberg
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 356
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Book Description
Author: Donald Nilan Marquardt
Publisher:
ISBN:
Category : Catalysts
Languages : en
Pages : 252
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Author: Jean-Marie Basset
Publisher: John Wiley & Sons
ISBN: 3527627103
Category : Science
Languages : en
Pages : 725
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Book Description
Covering everything from the basics to recent applications, this monograph represents an advanced overview of the field. Edited by internationally acclaimed experts respected throughout the community, the book is clearly divided into sections on fundamental and applied surface organometallic chemistry. Backed by numerous examples from the recent literature, this is a key reference for all chemists.
Author: Ian J S Fairlamb
Publisher: Royal Society of Chemistry
ISBN: 1849735832
Category : Reference
Languages : en
Pages : 285
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Book Description
A series of critical reviews and perspectives focussing on specific aspects of organometallic chemistry interfacing with other fields of study are provided. For this volume, the critical reviews cover topics such as the activation of "inert" carbon-hydrogen bonds, ligand design and organometallic radical species. For example, Charlie O'Hara discusses how mixed-metal compounds may perform the highly selective activation of C-H bonds and, in particular, how synergic relationships between various metals are crucial to this approach. The chemistry of a remarkable series of air-stable chiral primary phosphine ligands is discussed in some depth by Rachel Hiney, Arne Ficks, Helge M3ller-Bunz, Declan Gilheany and Lee Higham. This article focuses on the preparation of these ligands and also how they may be applied in various catalytic applications. Bas De Bruin reports on how ligand radical reactivity can be employed in synthetic organometallic chemistry and catalysis to achieve selectivity in radical-type transformations. As well as highlighting ligand-centered radical transformations in open-shell transition metals, an overview of the catalytic mechanism of Co(II)-catalysed olefin cyclopropanation is given, showing that enzyme-like cooperative metal-ligand-radical reactivity is no longer limited to real enzymes. Valuable and informative comprehensive reviews in the field of organometallic chemistry are also covered in this volume. For example, organolithium and organocuprate chemistry are reviewed by Joanna Haywood and Andrew Wheatley; aspects in Group 2 (Be-Ba) and Group 12 (Zn-Hg) compounds by Robert Less, Rebecca Melen and Dominic Wright; metal clusters by Mark Humphrey and Marie Cifuentes; and recent developments in the chemistry of the elements of Group 14 - focusing on low-coordination number compounds by Richard Layfield. This volume therefore covers many synthetic and applied aspects of modern organometallic chemistry which ought to be of interest to inorganic, organic and applied catalysis fields.
Author: Wolfgang A. Herrmann
Publisher: Georg Thieme Verlag
ISBN: 9783131151612
Category : Science
Languages : en
Pages : 258
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Book Description
The last in this ten-volume series, this text covers the most important standard compounds to be generally used in laboratories engaged in all branches of synthetic chemistry.
Author: F.R. Hartley
Publisher: Springer Science & Business Media
ISBN: 9400952473
Category : Science
Languages : en
Pages : 331
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Book Description
It is now IS years since the first patents in polymer supported metal complex catalysts were taken out. In the early days ion-exchange resins were used to support ionic metal complexes. Soon covalent links were developed, and after an initially slow start there was a period of explosive growth in the mid to late 1970s during which virtually every homogeneous metal complex catalyst ever reported was also studied bound to a support. Both polymers and inorganic oxides were studied as supports, although the great preponderance of workers studied polymeric supports, and of these polystyrene was by far the commonest used. This period served to show that by very careful design polymer-supported metal complex catalysts could have specific advantages over homogeneous metal complex catalysts. However the subject was a complicated one. Merely immobilising a successful metal complex catalyst to a functionalised support rarely yielded other than an inferior version of the catalyst. Amongst the many discouraging results of the 1970s, there were more than enough results that were sufficiently encouraging to demonstrate that, by careful design, supported metal complex catalysts could be prepared in which both the metal complex and the support combined together to produce an active catalyst which, due to the combination of support and complex, had advantages of activity, selectivity and specificity not found in homogeneous catalysts. Thus a new generation of catalysts was being developed.
Author: Catherine Jane Miller
Publisher:
ISBN:
Category : Organometallic compounds
Languages : en
Pages : 462
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Book Description
Author: C. Copéret
Publisher: Springer Science & Business Media
ISBN: 9783540264965
Category : Science
Languages : en
Pages : 312
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Book Description
With contributions by numerous experts
