Dioxygen Activation with Bis(arylimino)pyridine Radical Anion Complexes of Nickel PDF Download
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Author: Antonio David Manuel
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 111
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Book Description
The half-life of the reaction was not affected by deuterium labeling of the acetimino methyl groups but was affected by different substituents in the 4-position of the phenyl groups of the ligand. The reactions caused intraligand C-C bond cleavage with formation of a new C=O double bond, resulting in the complexes [Ni{6-(ArN=CMe)C5H3N-2-C(O)NAr}Cl] (where Ar = 4-X-2,6-iPr2C6H2 and X = H, Cl, or Br) and [Ni{6-(ArN=CCD3)C5H3N-2-C(O)NAr}Cl](where Ar = 2,6-iPr2C6H3). The structures of the complexes [Ni{6-(ArN=CR)C5H3N-2-C(O)NAr}Cl] (where Ar = 2,6-iPr2C6H3 and R = CH3 or CD3) were determined by X-ray crystallography. For all four complexes, the carboxamidato group was identified by a strong band in the infrared spectra assignable to the CO stretching vibration. Furthermore, the new carboxamidato ligands were removed from the metal center and isolated in their neutral form as 6-(ArN=CMe)C5H3N-2-C(O)NHAr (where Ar = 4-X-2,6-iPr2C6H2 and X = H, Cl, or Br) and 6-(ArN=CCD3)C5H3N-2-C(O)NHAr(where Ar = 2,6-iPr2C6H3). Taken together, these results indicate that the activation of dioxygen occurs at the ligand and without an overall oxidation state change at the Ni center. The observed ligand-centered oxygenation in these reactions contrasts with the prevailing metal-centered chemistry of redox-active bis(arylimino)pyridine complexes and demonstrates that they can be directly involved in the activation and conversion of a small molecule.
Author: Antonio David Manuel
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 111
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Book Description
The half-life of the reaction was not affected by deuterium labeling of the acetimino methyl groups but was affected by different substituents in the 4-position of the phenyl groups of the ligand. The reactions caused intraligand C-C bond cleavage with formation of a new C=O double bond, resulting in the complexes [Ni{6-(ArN=CMe)C5H3N-2-C(O)NAr}Cl] (where Ar = 4-X-2,6-iPr2C6H2 and X = H, Cl, or Br) and [Ni{6-(ArN=CCD3)C5H3N-2-C(O)NAr}Cl](where Ar = 2,6-iPr2C6H3). The structures of the complexes [Ni{6-(ArN=CR)C5H3N-2-C(O)NAr}Cl] (where Ar = 2,6-iPr2C6H3 and R = CH3 or CD3) were determined by X-ray crystallography. For all four complexes, the carboxamidato group was identified by a strong band in the infrared spectra assignable to the CO stretching vibration. Furthermore, the new carboxamidato ligands were removed from the metal center and isolated in their neutral form as 6-(ArN=CMe)C5H3N-2-C(O)NHAr (where Ar = 4-X-2,6-iPr2C6H2 and X = H, Cl, or Br) and 6-(ArN=CCD3)C5H3N-2-C(O)NHAr(where Ar = 2,6-iPr2C6H3). Taken together, these results indicate that the activation of dioxygen occurs at the ligand and without an overall oxidation state change at the Ni center. The observed ligand-centered oxygenation in these reactions contrasts with the prevailing metal-centered chemistry of redox-active bis(arylimino)pyridine complexes and demonstrates that they can be directly involved in the activation and conversion of a small molecule.
Author: Zhibin Guan
Publisher: Springer Science & Business Media
ISBN: 3540877509
Category : Science
Languages : en
Pages : 262
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Book Description
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.
Author: Marine Desage-El Murr
Publisher: John Wiley & Sons
ISBN: 352783088X
Category : Science
Languages : en
Pages : 373
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Book Description
Redox-Active Ligands Authoritative resource showcasing a new family of ligands that can lead to better catalysts and promising applications in organic synthesis Redox-Active Ligands gives a comprehensive overview of the unique features of redox-active ligands, describing their structure and synthesis, the characterization of their coordination complexes, and important applications in homogeneous catalysis. The work reflects the diversity of the subject by including ongoing research spanning coordination chemistry, organometallic chemistry, bioinspired catalysis, proton and electron transfer, and the ability of such ligands to interact with early and late transition metals, lanthanides, and actinides. The book is divided into three parts, devoted to introduction and concepts, applications, and case studies. After the introduction on key concepts related to the field, and the different types of ligands and complexes in which ligand-centered redox activity is commonly observed, mechanistic and computational studies are described. The second part focuses on catalytic applications of redox-active complexes, including examples from radical transformations, coordination chemistry and organic synthesis. Finally, case studies of redox-active guanidine ligands, and of lanthanides and actinides are presented. Other specific sample topics covered include: An overview of the electronic features of redox-active ligands, covering their historical perspective and biological background The versatility and mode of action of redox-active ligands, which sets them apart from more classic and tunable ligands such as phosphines or N-heterocyclic carbenes Preparation and catalytic applications of complexes of stable N-aryl radicals Metal complexes with redox-active ligands in H+/e- transfer transformations By providing up-to-date information on important concepts and applications, Redox-Active Ligands is an essential reading for researchers working in organometallic and coordination chemistry, catalysis, organic synthesis, and (bio)inorganic chemistry, as well as newcomers to the field.
Author: Gerard van Koten
Publisher: Springer
ISBN: 3642310818
Category : Science
Languages : en
Pages : 363
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Book Description
Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostál: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kálmán J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.
Author: Wilson D. Shafer
Publisher: MDPI
ISBN: 303928388X
Category : Science
Languages : en
Pages : 414
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Book Description
Since the turn of the last century when the field of catalysis was born, iron and cobalt have been key players in numerous catalysis processes. These metals, due to their ability to activate CO and CH, haev a major economic impact worldwide. Several industrial processes and synthetic routes use these metals: biomass-to-liquids (BTL), coal-to-liquids (CTL), natural gas-to-liquids (GTL), water-gas-shift, alcohol synthesis, alcohol steam reforming, polymerization processes, cross-coupling reactions, and photocatalyst activated reactions. A vast number of materials are produced from these processes, including oil, lubricants, waxes, diesel and jet fuels, hydrogen (e.g., fuel cell applications), gasoline, rubbers, plastics, alcohols, pharmaceuticals, agrochemicals, feed-stock chemicals, and other alternative materials. However, given the true complexities of the variables involved in these processes, many key mechanistic issues are still not fully defined or understood. This Special Issue of Catalysis will be a collaborative effort to combine current catalysis research on these metals from experimental and theoretical perspectives on both heterogeneous and homogeneous catalysts. We welcome contributions from the catalysis community on catalyst characterization, kinetics, reaction mechanism, reactor development, theoretical modeling, and surface science.
Author: David J. Leggett
Publisher: Springer Science & Business Media
ISBN: 1468449346
Category : Science
Languages : en
Pages : 488
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Book Description
This volume is concerned with methods that are available for the calculation of for mation constants, in particular computational procedures. Although graphical meth ods have considerable value in the exploration of primary (raw) data they have been overtaken by computational methods, which, for the most part, take primary data and return the refined formation constants. Graphical methods are now considered com plementary to these general computational procedures. This volume brings together programs that span the lifetime of computer-assisted determination of formation constants. On one hand the reader will find listings of programs that are derived from LETAGROP (b.l961) and the GAUSS-G/SCOGS (b. 1962) families. On the other hand programs are presented that are the newest mem bers of the SCOGS lineage and from the on-going MINIQUAD series. One program is presented that describes a computational approach to the classical Hedstrom Osterberg methods; another that takes care of electrode calibration in a simple yet rigorous manner. Potentiometry and spectrophotometry are the most popular experimental tech niques for equilibrium studies, and the programs in this volume reflect this. Four programs handle potentiometric data, two will process spectrophotometric data, and one makes use of both types of data separately or in combination.
Author: Mariam Al-Ali AlMa'adeed
Publisher: Springer
ISBN: 3319259822
Category : Technology & Engineering
Languages : en
Pages : 354
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Book Description
This book describes industrial applications of polyolefins from the researchers' perspective. Polyolefins constitute today arguably the most important class of polymers and polymeric materials for widespread industrial applications. This book summarizes the present state of the art. Starting from fundamental aspects, such as the polymerization techniques to synthesize polyolefins, the book introduces the topic. Basic knowledge about polyolefin composites and blends is explained, before applications aspects in different industry sectors are discussed. The spectrum comprises a wide range of applications and industry sectors, such as the packaging and food industry, the textile industry, automotive and buildings, and even biomedical applications. Topics, which are addressed in the various chapters, comprise synthesis and processing of the materials; their classification; mechanical, physical and technical requirements and properties; their characterization; and many more. In the end of the book, even the disposal, degradation and recycling of polyolefins are addressed, and light is shed on their commercial significance and economic value. In this way, the book follows the entire 'lifetime' of polyolefin compounds and materials: from their synthesis and processing, over applications, to the recycling and reuse of disposed or degraded polyolefin substrates.
Author: José A. Martinho Simões
Publisher: Springer Science & Business Media
ISBN: 9400900996
Category : Science
Languages : en
Pages : 313
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Book Description
Author: S. C. GUPTA
Publisher: PHI Learning Pvt. Ltd.
ISBN: 8120350650
Category : Technology & Engineering
Languages : en
Pages : 682
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Book Description
This textbook, now in the second edition, offers a completely up-to-date and in-depth introduction to the principles and applications of optoelectronic devices and systems. The text gives a detailed description of optical fibre waveguides, optical fibre cables and their characteristics, manufacturing process and drawing of optical fibres. In addition, it deals with photon sources, photon detectors, fibre optics as a medium and LAN and WAN systems, short and long haul optical fibre communication systems, electro-optic modulators and their characteristics. The second edition possesses a new section on Optical Fibre Based Broadband High Speed Network in Chapter 8, thus highlighting an updated version. Apart from this, a new chapter on Intensity Dependent Refractive Index Effect has been introduced into the text that discusses the effect of focusing on spatial and temperature profiles in a non-linear crystal medium. This chapter further explains the various physical phenomena like the creation of sharp opaque filaments, irradiation induced damaging of the crystal, oscillatory waveguide propagation, saturation effects and other properties in detail. Primarily intended for the undergraduate students of electronics and communication engineering, the book should also prove extremely useful for the postgraduate students of physics. Key features • Provides comprehensive explanation of optical fibre communication with illustrations. • Gives extensive theory and experimental and holographic applications. • Discusses the applications of lasers in industry, military and medical as well as fibre optics applications. • Describes optical computing, optical gates and their applications with illustrations. • Includes solved numericals at the end of book for better understanding of topics.
Author: Gary O. Spessard
Publisher: Oxford University Press, USA
ISBN: 9780199342679
Category : Chemistry, Organic
Languages : en
Pages : 0
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Book Description
Designed with the needs of both undergraduate and graduate students in mind, Organometallic Chemistry, Third Edition, covers the fundamentals of organometallic chemistry by presenting seminal experiments, analyzing real data, and offering the most comprehensive problem sets available. The text opens with careful explanations of the structure and bonding of organometallic compounds, providing a uniquely accessible introduction to the subject for undergraduate students. Later chapters build on this foundation with in-depth coverage of more advanced topics such as organometallic reaction mechanisms, catalysis, carbene complexes, metathesis, applications of organometallic chemistry to organic synthesis, and bioorganometallic chemistry.
