Download or read book Z selective Olefin Metathesis Processes and Cis syndioselective ROMP with High Oxidation State Molybdenum Alkylidenes written by Margaret McGuigan Flook and published by . This book was released on 2012 with total page 215 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 1: Reaction of W(CCMe3)Cl 3(dme) with one equivalent of (3,5-Me 2C6H3NCH2CH 2)3N)Li3 affords yellow, crystalline W(CCMe3)(N3N) in good yield. The reactivity of this new alkylidyne complex towards terminal alkynes was investigated. Two other new tungsten alkylidynes, W(CCMe3)(pyr) 3 (pyr = 2,5-dimethylpyrrolide) and W(CCMe3)(Ph 2N)3 were prepared by the addition of three equivalents of lithium dimethylpyrrolide or lithium diphenylamide, respectively, to W(CCMe3)Cl 3(dme). The reactivity of these new alkylidynes with various alcohols is reported. The reactivity of several tungsten alkylidyne compounds towards ligand displacement by surface silanols is reported, resulting in the synthesis of several new silicasupported tungsten alkylidynes. The alkyne metathesis activity of all new homogeneous and heterogeneous alkylidyne complexes is reported. Chapter 2: Addition of one equivalent of 2,4,6,2',4',6'-hexaisopropylterphenol to Mo(NAd)(CHCMe 2Ph)(pyr)2 results in the formation of Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (HIPTO = hexaisopropylterphenoxide). This new alkylidene compound was found to catalyze the metathesis of 1-hexene in 20% yield to 95% cis 5-decene, which represents the first report of highly Z-selective metathesis homocoupling of a terminal olefin. The decomposition of the catalyst in the presence of ethylene is explored. The syntheses of several new bulky achiral phenoxide ligands are presented, along with the syntheses of the corresponding MAP (monoalkoxide monopyrrolide) molybdenum imido alkylidene compounds. The reactivity of new MAP compounds containing bulky phenoxide ligands towards the Z-selective metathesis of terminal and internal olefins is presented. The cis-selectivity of this system is proposed to arise from the combination of a relatively small imido ligand in conjunction with a very bulky alkoxide forcing the substituents of the substrate to point in this same direction with each insertion. Photolysis of MAP compounds with 366 nm radiation was found to produce significant amounts of anti alkylidenes, and the kinetics of decay of unstable anti alkylidenes are investigated. Chapter 3: The reaction of 2,3-dicarbomethoxynorbomadiene (DCMNBD) with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (Ad = 1-adamantyl, HIPTO = hexaisopropylterphenoxide) affords >98% cis, >98% tactic polyDCMNBD. The tacticity of this polymer is proved to be syndiotactic through polymerization of DCMenthNBD (2,3-dicarbomenthoxynorbomadiene) and IH- H COSY. A variety of related MAP alkylidene compounds are also investigated towards the ROMP of DCMNBD and found to produce polyDCMNBD in a range of tacticities and cis contents. Highly cis polyNBDF6 (poly-bis(CF 3)-norbomadiene) was also prepared using molybdenum MAP compounds, and the resulting polymer was found to be essentially insoluble in common organic solvents. Solid state CPMAS 13C NMR spectroscopy revealed insoluble polyNBDF6 to be highly tactic, and the tacticity is proposed to be syndiotactic. Cis, tactic polymer was prepared through the addition of 3,3-methylphenylcyclopropene (MPCP) to molybdenum MAP compounds. Attempts towards determination of the tacticity of cispolyMPCP are presented, including the synthesis of three 3,3-disubstituted cyclopropene monomers containing chiral tags. The cis-selective ROMP of cyclooctene and 1,5- cyclooctadiene are reported. The syndioselectivity of the catalysts is proposed to be controlled by the configuration of the 4-coordinate metal center, which alternates with each insertion of monomer. Chapter 4: Racemic 2,3-dicarbomethoxynorbornene (rac-DCMNBE) is polymerized by Mo(NAd)(CHCMe 2Ph)(pyr)(HMTO) (Ad = 1-adamantyl, pyr = pyrrolide, HMTO = hexamethylterphenoxide) to afford an all-cis polymer that is syndiotactic and composed of alternating enantiomers. The cis, syndiotactic ROMP of several other racemic chiral monomers are reported, also affording structures containing a high degree of enantiomer alteration. Attempts towards the alternating copolymerization of two different monomers are reported. The ROMP of enantiomerically pure (+)-dicarbomethoxynorbornene with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) leads to the production of 92% trans-isotactic polyDCMNBE. The structure of trans-isotactic polyDCMNBD is proved through hydrogenation and comparison of its 3C NMR spectrum with that of known cis-isotactic polyDCMNBE. Both cis/syndiotactic/alternating poly-rac-DCMNBE and trans/isotactic poly-(+)-DCMNBE are polymer structures that have not been previously reported. The thermal properties of all new polymers and their hydrogenated counterparts are reported and are found to correlate closely with polymer structure.
Download or read book Handbook of Metathesis Volume 1 written by Robert H. Grubbs and published by John Wiley & Sons. This book was released on 2015-02-18 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: The second edition of the Handbook of Metathesis, edited by Nobel Prize Winner Robert H. Grubbs and his team, is available as a 3 Volume set as well as individual volumes. Volume 1, edited by R. H. Grubbs together with A. G. Wenzel focusses on Catalyst Development and Mechanism. The new edition of this set is completely updated (more than 80% new content) and expanded, with a special focus on industrial applications. Written by the "Who-is-Who" of metathesis, this book gives a comprehensive and high-quality overview. It is the perfect and ultimate one-stop-reference source in this field and indispensable for chemists in academia and industry alike. View the set here - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527334246.html Other available volumes: Volume 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O´Leary - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html Volume 3: Polymer Synthesis, Editors: R. H. Grubbs and E. Khosravi - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339507.html
Download or read book Handbook of Metathesis 3 Volume Set written by Robert H. Grubbs and published by John Wiley & Sons. This book was released on 2015-05-26 with total page 1639 pages. Available in PDF, EPUB and Kindle. Book excerpt: Covering the complete breadth of the olefin metathesis reaction. The second edition of the ultimate reference in this field is completely updated and features more than 80% new content, with the focus on new developments in the field, especially in industrial applications. No other book covers the topic in such a comprehensive manner and in such high quality, and this new edition retains the three-volume format: Catalyst Development, Applications in Organic Synthesis and Polymer Synthesis. Edited by a Nobel laureate in the field, and with a list of contributors that reads like a "Who's-Who" of metathesis, this is an indispensable one-stop reference for organic, polymer and industrial chemists, as well as chemists working with organometallics. Individual volumes also available separately to purchase Volume 1: Catalyst Development - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339485.html Volume 2: Applications in Organic Synthesis - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html Volume 3: Polymer Synthesis - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339507.html
Download or read book High oxidation state Molybdenum and Tungsten Monoalkoxide Pyrrolide Alkylidenes as Catalysts for Olefin Metathesis written by Erik Matthew Townsend and published by . This book was released on 2014 with total page 195 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 1 describes work toward solid-supported W olefin metathesis catalysts. Attempts to tether derivatives of the known Z-selective catalyst W(NAr)(C3H6)(pyr)(OHIPT) (Ar = 2,6- diisopropylphenyl, pyr = pyrrolide; HIPT = 2,6-bis-(2,4,6-triisopropylphenyl)phenyl) to a modified silica surface by covalent linkages are unsuccessful due to destructive interactions between W precursors and silica. W(NAr)(C3H6)(pyr)(OHIPT) and W(NAr)(CHCMe2Ph)(pyr)(OHIPT-NMe2) (HIPT-NMe 2 = 2,6-bis-(2,4,6-triisopropylphenyl)-4- dimethylaminophenyl) are adsorbed onto calcined alumina. W(NAr)(C 3H6 )(pyr)(OHIPT) is destroyed upon binding to alumina, while W(NAr)(CHCMe 2Ph)(pyr)(OHIPT-NMe 2) appears to bind through a non-destructive interaction between the dimethylamino group and an acidic surface site. The heterogeneous catalysts perform non-stereoselective metathesis of terminal olefins, and W(NAr)(CHCMe2Ph)(pyr)(OHIPT-NMe2) can be washed off the surface with polar solvent and perform solution-phase Z-selective metathesis. Chapter 2 details selective metathesis homocoupling of 1,3-dienes with Mo and W monoalkoxide pyrrolide (MAP) catalysts. A catalytically relevant vinylalkylidene complex, Mo(NAr)(CHCHCH(CH3)2)(Me2pyr)(OHMT) (HMT = 2,6-bis(2,4,6-trimethylphenyl)phenyl; Me2pyr = 2,5-dimethylpyrrolide), is isolated. A series of Mo and W MAP catalysts is synthesized and tested for activity, stereoselectivity, and chemoselectivity in 1,3-diene metathesis homocoupling. Catalysts containing the OHIPT ligand display excellent selectivity in general, and W catalysts are less active but more selective than their Mo counterparts. Chapter 3 recounts the synthesis and characterization of several heteroatom-substituted alkylidene complexes with the formula Mo(NAr)(CHER)(Me2pyr)(OTPP) (TPP = 2,3,5,6- tetraphenylphenyl; ER = OPr, N-pyrrolidinonyl, N-carbazolyl, pinacolborato, trimethylsilyl, SPh, or PPh2). Synthesis proceeds via alkylidene exchange between Mo(NAr)(CHR)(Me2pyr)(OTPP) (R = H, CMe2Ph) and a CH2CHER precursor. Each complex behaves similarly to known MAP complexes in olefin metathesis processes; the electronic identity of ER has little effect on catalytic properties. Distinctive features of alkylidene isomerism and catalyst resting state are examined. Chapter 4 contains synthetic and catalytic studies of thiolate-containing Mo and W imido alkylidene complexes. The species M(NAr)(CHCMe 2Ph)(pyr)(SHMT) (M = Mo or W), Mo(NAr)(CHCMe2Ph)(Me2pyr)(STPP), and Mo(NAr)(CHCMe2Ph)(STPP)2 are synthesized by substitution of the appropriate thiol or thiolate ligands for pyrrolide or triflate ligands in metal precursors. These complexes show similar structural and spectral characteristics to alkoxidecontaining species. The thiolate complexes and their alkoxide analogues are compared for activity and selectivity in metathesis homocoupling and ring-opening metathesis polymerization processes. In general, thiolate catalysts are slower and less selective than alkoxide catalysts.
Download or read book High Oxidation State N heterocyclic Carbene Molybdenum Alkylidene Complexes Functional group Tolerant Olefin Metathesis Catalysts written by Suman Sen and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Comprehensive Coordination Chemistry II written by J. A. McCleverty and published by Newnes. This book was released on 2003-12-03 with total page 11845 pages. Available in PDF, EPUB and Kindle. Book excerpt: Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.
Download or read book Late Transition Metal Polymerization Catalysis written by Bernhard Rieger and published by John Wiley & Sons. This book was released on 2006-03-06 with total page 345 pages. Available in PDF, EPUB and Kindle. Book excerpt: At the start of the 1950s, Ziegler and Natta discovered that simple metallorganic catalysts are capable of transforming olefins into linear polymers with highly ordered structures. This pioneering discovery was recognized with a Nobel Prize in 1963. In the 80s and 90s, the development of molecular defined metallocenes led to a renaissance for non-polar polyolefin materials. Designer catalysts allowed a greater precision in defining properties of the material. The past 10 years have seen the discovery of new catalysts based on late transition metals, which allow the combination of polar monomers with non-polar olefins and thus lead to innovative materials. Here, the world's leading authors from industry and academia describe the latest developments in this fascinating field for the first time in such comprehensive detail. In so doing, they introduce readers systematically to the basic principles and show how these new catalysts can effectively be used for polymerization reactions. This makes the book an ideal and indispensable reference for specialists, advanced students, and scientists of various disciplines dealing with research into catalysts and materials science.
Download or read book Olefin Metathesis written by Karol Grela and published by . This book was released on 2014 with total page 608 pages. Available in PDF, EPUB and Kindle. Book excerpt: This is a complete examination of the theory and methods of modern olefin metathesis, one of the most widely used chemical reactions in research and industry. Provides basic information for non-specialists, while also explaining the latest trends and advancements in the field to experts Discusses the various types of metathesis reactions, including CM, RCM, enyne metathesis, ROMP, and tandem processes, as well as their common applications Outlines the tools of the trade--from the important classes of active metal complexes to optimal reaction conditions--and suggests practical solutions for common reaction problems Includes tables with structures of commercial catalysts, and recommendations for commercial catalyst suppliers
Download or read book Olefin Metathesis and Metathesis Polymerization written by K. J. Ivin and published by Elsevier. This book was released on 1997-01-07 with total page 489 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials science and chemical engineering. Discusses different classes of olefin metathesis and the choice of reaction conditions and catalyst Considers commercial processes with examples from existing and new technologies Provides a complete overview of the subject from its beginning to the present day
Download or read book Alkene Metathesis in Organic Synthesis written by Alois Fuerstner and published by Springer. This book was released on 2003-07-01 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organometallic chemistry is a well established research area at the interface of organic and inorganic chemistry. In recent years this field has undergone a ren aissance as our understanding of organometallic structure, properties and mechanism has opened the way for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as medicine, biology, materials and polymer sciences and organic synthesis. For example, in the de velopment of new catalytic processes, organometallic chemistry is helping meet the challenge to society that the economic and environmental necessities of the future pose. As this field becomes increasingly interdisciplinary, we recognize the need for critical overviews of new developments that are of broad significance. This is our goal in starting this new series Topics in Organometallic Chemistry. The scope of coverage includes a broad range of topics of pure and applied or ganometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. Topics in Organometallic Chemistry differs from existing review series in that each volume is thematic, giving an overview of an area that has reached a stage of maturity such that coverage in a single review article is no longer possible. Furthermore, the treatment addresses a broad audience of researchers, who are not specialists in the field, starting at the graduate student level. Discussion of possible future research directions in the areas covered by the individual volumes is welcome.
Download or read book Metal Catalysts in Olefin Polymerization written by Zhibin Guan and published by Springer Science & Business Media. This book was released on 2009-03-31 with total page 262 pages. Available in PDF, EPUB and Kindle. Book excerpt: Polyolefin is a major industry that is important for our economy and impacts every aspect of our lives. The discovery of new transition metal-based catalysts is one of the driving forces for the further advancement of this field. Whereas the classical heterogeneous Ziegler-Natta catalysts and homogeneous early transition metal metallocene catalysts remain the workhorses of the polyolefin industry, in roughly the last decade, tremendous progress has been made in developing non-metallocene-based olefin polymerization catalysts. Particularly, the discovery of late transition metal-based olefin polymerization catalysts heralds a new era for this field. These late transition metal complexes not only exhibit high activities rivaling their early metal counterparts, but more importantly they offer unique properties for polymer architectural control and copolymerization with polar olefins. In this book, the most recent major breakthroughs in the development of new olefin polymerization catalysts, including early metal metallocene and non-metallocene complexes and late transition metal complexes, are discussed by leading experts. The authors highlight the most important discoveries in catalysts and their applications in designing new polyolefin-based functional materials.
Download or read book Stereoselective Polymerization with Single Site Catalysts written by Lisa S. Baugh and published by CRC Press. This book was released on 2007-11-29 with total page 698 pages. Available in PDF, EPUB and Kindle. Book excerpt: New synthetic techniques allow chemists to modify polymer microstructures more precisely than ever, making it possible to design materials that meet increasingly demanding performance requirements. Written and edited by experts in the field, Stereoselective Polymerization with Single-Site Catalysts reviews how the relative stereochemistry of
Download or read book A Companion to Contemporary Design since 1945 written by Anne Massey and published by John Wiley & Sons. This book was released on 2019-03-26 with total page 512 pages. Available in PDF, EPUB and Kindle. Book excerpt: A critical overview of contemporary design and its place within the broader context of art history A Companion to Contemporary Design since 1945 introduces readers to a collection of specially commissioned essays exploring the complex areas of design that emerged through the latter half of the twentieth century, design history, design methods, design studies and more recently, design thinking. The book delivers a thoughtful overview of all design disciplines and also strives to stimulate inter-disciplinary debate and examine unconsidered convergences among design applications in different fields. By offering a new perspective on design, the articles assembled here present a challenging account of the boundaries between design history and its cognate disciplines, especially art history. The volume comprises five sections—Time, Place, Space, Objects and Audiences—that discuss environments for design and how we interact with designed objects and spaces. Notable features include: 24 new essays reflecting the current state of design history and theory, and examining developments on a global basis Contributions by eminent scholars and practitioners from around the globe Enriched throughout with illustrations A Companion to Contemporary Design since 1945 provides a new and thought-provoking revision of our conception and understanding of contemporary design that will be essential reading for students at both undergraduate and graduate levels as well as researchers and teachers working in design history, theory and practice, and in related fields.
Download or read book Sound and Vibration Damping with Polymers written by American Chemical Society. Meeting and published by . This book was released on 1990 with total page 488 pages. Available in PDF, EPUB and Kindle. Book excerpt: Here is the first modern text that treats sound and vibration damping from a united point of view. It focuses on the development and use of polymers for sound and vibration damping, with applications primarily in the marine, automotive, appliance, and machinery areas. Blends and interpenetrating networks are addressed for their ability to damp over broad temperature and frequency ranges. Also includes several review papers which develop fundamental points of view, both scientific and engineering.
Download or read book Ring Opening Metathesis Polymerisation and Related Chemistry written by Ezat Khosravi and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 489 pages. Available in PDF, EPUB and Kindle. Book excerpt: Since the last ASI in Turkey in Sept. 1995, the olefin metathesis has made remarkable strong developments with an incredible speed in various directions. New catalyst systems have been developed which have resulted in the synthesis of novel materials. Other fascinating developments have been the new catalysts for stereoselective metathesis and catalysts with considerable functional group tolerance. These new catalysts in addition to Ring Opening Metathesis Polymerisation (ROMP) and Acyclic Diene Metathesis (ADMET) are now powerful tools for Ring Closing Metathesis (RCM) and have found many applications in the synthesis of natural products. A lot of information has been established about all aspects of the olefin metathesis and there is a vast literature concerning the process, covering the initiators, mechanistic features and applications of this reaction in organic and polymer synthesis. The NATO ASI on rd th ROMP and Related Chemistry took place in Polanica-Zdroj, Poland during 3 to 15 Sept. 2000, to highlight the developments in this area and to discuss the prospects and visions for the year 2000 and beyond. The aims of the ASI were: to provide a platform for dissemination of knowledge; to promote communication between people who have a serious interest in this field of chemistry; to help establishing international scientific contacts and to provide an opportunity for the scientists with an appropriate scientific background to learn of recent developments in this field of science. There were 15 lecturers and 67 participants in this NATO ASI.
Download or read book Handbook of Polyolefins written by Cornelia Vasile and published by CRC Press. This book was released on 2000-06-21 with total page 1040 pages. Available in PDF, EPUB and Kindle. Book excerpt: A handbook on polyolefins. This second edition includes new material on the structure, morphology and properties of polyolefin (PO) synthesis. It focuses on synthetic advances, the use of additives, special coverage of PO blends, composites and fibres, and surface treatments. It also addresses the problem of interfacial and superficial phenomena.
Download or read book Applied Homogeneous Catalysis written by Arno Behr and published by John Wiley & Sons. This book was released on 2012-04-16 with total page 717 pages. Available in PDF, EPUB and Kindle. Book excerpt: Auf fortgeschrittenem Niveau und mit didaktischem Anspruch bietet Ihnen dieser Band zahlreiche Fragen mit Antworten und eine breite Palette von Fallstudien aus der Industrie, ergänzt durch weiterführende Literaturhinweise und Referenzen der Originalliteratur. Insbesondere geht es um die modernsten katalytischen Prozesse mit ihren Anwendungen in der Pharmazie und der Feinchemikalien-Industrie, wobei auch kommerzielle Aspekte besprochen werden. Der Autor, ein erfahrener Dozent mit Industriepraxis, legt Chemikern und Chemieingenieuren damit ein praxistaugliches Hilfsmittel vor.
