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Pincer Metal Complexes

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Pincer Metal Complexes

Pincer Metal Complexes Book
Author : Akshai Kumar
Publisher : Elsevier
Release : 2021-11-26
ISBN : 0128220910
Language : En, Es, Fr & De

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Book Description :

Pincer-Metal Complexes: Applications in Catalytic Dehydrogenation Chemistry provides an overview of pincer-metal catalytic systems that transform hydrocarbons and their derivatives from an synthetic and mechanistic point-of-view. This book provides thorough coverage of the operating mechanisms and dehydrogenation catalyst compatibility in both functionalized and unfunctionalized hydrocarbon systems. In addition, it includes success stories of pincer-metal systems, as well as current and future challenges. The book is an ideal reference for researchers practicing synthetic organic chemistry, inorganic chemistry, organometallic chemistry and catalysis in academia and industry. In recent years there has been a surge in the research on hydrocarbon dehydrogenation catalytic systems that are compatible with polar substituents. This helps facilitate formulation of tandem processes that are not limited to hydrocarbon transformation but also to hydrocarbon functionalization in a single pot. Covers applications of pincer-metal complexes in organic transformations Includes pincer-group 8 and 9 metal complexes for alkane dehydrogenations Features a discussion of pincer-metal complexes for the dehydrogenation of functionalized hydrocarbons and electro-catalytic transformations

The Chemistry of Pincer Compounds

The Chemistry of Pincer Compounds Book
Author : David Morales-Morales,Craig G.M. Jensen
Publisher : Elsevier
Release : 2011-08-11
ISBN : 9780080545158
Language : En, Es, Fr & De

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Book Description :

Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties. The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials. * Describes the chemistry and applications of this important class of organometallic and coordination compounds * Covers the areas in which pincer complexes have had an impact * Includes information on more recent and interesting pincer compounds not just those that are well-known

Pincer Compounds

Pincer Compounds Book
Author : David Morales-Morales
Publisher : Elsevier
Release : 2018-04-11
ISBN : 0128129328
Language : En, Es, Fr & De

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Book Description :

Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen’s The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. Describes the chemistry and applications of this important class of organometallic and coordination compounds Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry

Pincer and Pincer Type Complexes

Pincer and Pincer Type Complexes Book
Author : Kálmán J. Szabó
Publisher : John Wiley & Sons
Release : 2014-08-25
ISBN : 9783527334421
Language : En, Es, Fr & De

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Book Description :

This new book on this hot topic summarizes the key achievements for the synthesis and catalytic applications of pincer and pincer-type complexes, providing readers with the latest research highlights. The editors have assembled an international team of leaders in the field, and their contributions focus on the application of various pincer complexes in modern organic synthesis and catalysis, such as C-C and C-X bond forming reactions, C-H bond functionalization, and the activation of small molecules, as well as asymmetric catalysis. A must-have for every synthetic chemist in both academia and industry intending to develop new catalysts and improved synthetic protocols.

Organometallic Pincer Chemistry

Organometallic Pincer Chemistry Book
Author : Gerard van Koten,David Milstein
Publisher : Springer
Release : 2012-09-17
ISBN : 3642310818
Language : En, Es, Fr & De

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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.

The Privileged Pincer Metal Platform Coordination Chemistry Applications

The Privileged Pincer Metal Platform  Coordination Chemistry   Applications Book
Author : Gerard van Koten,Robert A Gossage
Publisher : Springer
Release : 2015-08-27
ISBN : 3319229273
Language : En, Es, Fr & De

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Book Description :

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

Pincer Metal Complexes

Pincer Metal Complexes Book
Author : Akshai Kumar
Publisher : Elsevier
Release : 2021-11-12
ISBN : 0128220929
Language : En, Es, Fr & De

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Book Description :

Pincer-Metal Complexes: Applications in Catalytic Dehydrogenation Chemistry provides an overview of pincer-metal catalytic systems that transform hydrocarbons and their derivatives from an synthetic and mechanistic point-of-view. This book provides thorough coverage of the operating mechanisms and dehydrogenation catalyst compatibility in both functionalized and unfunctionalized hydrocarbon systems. In addition, it includes success stories of pincer-metal systems, as well as current and future challenges. The book is an ideal reference for researchers practicing synthetic organic chemistry, inorganic chemistry, organometallic chemistry and catalysis in academia and industry. In recent years there has been a surge in the research on hydrocarbon dehydrogenation catalytic systems that are compatible with polar substituents. This helps facilitate formulation of tandem processes that are not limited to hydrocarbon transformation but also to hydrocarbon functionalization in a single pot. Covers applications of pincer-metal complexes in organic transformations Includes pincer-group 8 and 9 metal complexes for alkane dehydrogenations Features a discussion of pincer-metal complexes for the dehydrogenation of functionalized hydrocarbons and electro-catalytic transformations

Organometallic Chemistry and Catalysis

Organometallic Chemistry and Catalysis Book
Author : Didier Astruc
Publisher : Springer Science & Business Media
Release : 2007-08-02
ISBN : 3540461280
Language : En, Es, Fr & De

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Book Description :

This volume covers both basic and advanced aspects of organometallic chemistry of all metals and catalysis. In order to present a comprehensive view of the subject, it provides broad coverage of organometallic chemistry itself. The catalysis section includes the challenging activation and fictionalization of the main classes of hydrocarbons and the industrially crucial heterogeneous catalysis. Summaries and exercises are provides at the end of each chapter, and the answers to these exercises can be found at the back of the book. Beginners in inorganic, organic and organometallic chemistry, as well as advanced scholars and chemists from academia and industry will find much value in this title.

CO2 Hydrogenation Catalysis

CO2 Hydrogenation Catalysis Book
Author : Yuichiro Himeda
Publisher : John Wiley & Sons
Release : 2021-03-29
ISBN : 3527346635
Language : En, Es, Fr & De

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Book Description :

A guide to the effective catalysts and latest advances in CO2 conversion in chemicals and fuels Carbon dioxide hydrogenation is one of the most promising and economic techniques to utilize CO2 emissions to produce value-added chemicals. With contributions from an international team of experts on the topic, CO2 Hydrogenation Catalysis offers a comprehensive review of the most recent developments in the catalytic hydrogenation of carbon dioxide to formic acid/formate, methanol, methane, and C2+ products. The book explores the electroreduction of carbon dioxide and contains an overview on hydrogen production from formic acid and methanol. With a practical review of the advances and challenges in future CO2 hydrogenation research, the book provides an important guide for researchers in academia and industry working in the field of catalysis, organometallic chemistry, green and sustainable chemistry, as well as energy conversion and storage. This important book: Offers a unique review of effective catalysts and the latest advances in CO2 conversion Explores how to utilize CO2 emissions to produce value-added chemicals and fuels such as methanol, olefins, gasoline, aromatics Includes the latest research in homogeneous and heterogeneous catalysis as well as electrocatalysis Highlights advances and challenges for future investigation Written for chemists, catalytic chemists, electrochemists, chemists in industry, and chemical engineers, CO2 Hydrogenation Catalysis offers a comprehensive resource to understanding how CO2 emissions can create value-added chemicals.

Metal Ligand Co operativity

Metal Ligand Co operativity Book
Author : Gerard van Koten,Karl Kirchner,Marc-Etienne Moret
Publisher : Springer Nature
Release : 2021-03-29
ISBN : 3030689166
Language : En, Es, Fr & De

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Book Description :

This book provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of significant recent developments in the area of metal-ligand cooperativity, with a focus on pincer architectures. The various contributions highlight the widespread impact of M–L co-operativity phenomena on modern organometallic chemistry and catalyst development. The development of efficient and selective catalytic transformations relies on the understanding and fine control of the various elementary reactions that constitutes a catalytic cycle. Co-operative ligands, which actively participate in bond making and bond breaking together to the metal they support, open up new avenues in this area. In particular, buttressing a weak or reactive metal-ligand bond by flanking coordinating arms in a pincer ligand design is proving a versatile strategy to access robust metal complexes that exhibit unusual and selective reactivity patterns.

Transition Metal Dinitrogen Complexes

Transition Metal Dinitrogen Complexes Book
Author : Yoshiaki Nishibayashi
Publisher : John Wiley & Sons
Release : 2019-05-06
ISBN : 352734425X
Language : En, Es, Fr & De

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Book Description :

A comprehensive book that explores nitrogen fixation by using transition metal-dinitrogen complexes Nitrogen fixation is one of the most prominent fields of research in chemistry. This book puts the focus on the development of catalytic ammonia formation from nitrogen gas under ambient reaction conditions that has been recently repowered by some research groups. With contributions from noted experts in the field, Transition Metal-Dinitrogen Complexes offers an important guide and comprehensive resource to the most recent research and developments on the topic of nitrogen fixation by using transition metal-dinitrogen. The book is filled with the information needed to understand the synthesis of transition metal-dinitrogen complexes and their reactivity. This important book: -Offers a resource for understanding nitrogen fixation chemistry that is essential for explosives, pharmaceuticals, dyes, and all forms of life -Includes the information needed for anyone interested in the field of nitrogen fixation by using transition metal-dinitrogen complexes -Contains state-of-the-art research on synthesis of transition metal-dinitrogen complexes and their reactivity in nitrogen fixation -Incorporates contributions from well-known specialists and experts with an editor who is an innovator in the field of dinitrogen chemistry Written for chemists and scientists with an interest in nitrogen fixation, Transition Metal-Dinitrogen Complexes is a must-have resource to the burgeoning field of nitrogen fixation by using transition metal-dinitrogen complexes.

Copper I Chemistry of Phosphines Functionalized Phosphines and Phosphorus Heterocycles

Copper I  Chemistry of Phosphines  Functionalized Phosphines and Phosphorus Heterocycles Book
Author : Maravanji S. Balakrishna
Publisher : Elsevier
Release : 2019-04-25
ISBN : 0128156945
Language : En, Es, Fr & De

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Book Description :

Copper(I) Complexes of Phosphines, Functionalized Phosphines and Phosphorus Heterocycles is a comprehensive guide to one of the most widely used and extensively studied metals: copper. The numerous practical applications of copper compounds are discussed, including homogeneous and heterogeneous catalysis and their use as fungicides, pesticides, pigments for paints, resins and glasses, and in high-temperature superconductors. The remarkable structural flexibility of simple copper(I) complexes, such as cuprous halides is covered, including numerous structural motifs that, when combined with different ligand systems, exhibit linear, trigonal planar or tetrahedral geometries. This work is an essential reference for inorganic and coordination chemists, as well as researchers working on catalysis, anticancer reagents, luminescence, fluorescence and photophysical aspects. Discusses the properties of copper and similarities to noble metals, such as their corrosion resistance, high thermal and electrical conductivity and rich coordination chemistry Includes the copper(I) coordination chemistry of tertiary phosphines, bisphosphines and phosphines containing other donor atoms and their potential application in catalysis, biosystems and photochemical areas Features a discussion of the rich photochemistry exhibited by some mixed-ligand copper(I) complexes (phosphines with heteroaromatic ligands) which can exhibit coprophilic interactions, photoluminescence and thermochromic properties

Unconventional Pincer Ligands and Their Transition Metal Complexes

Unconventional Pincer Ligands and Their Transition Metal Complexes Book
Author : Caitlin McQueen
Publisher : Unknown
Release : 2013
ISBN : 0987650XXX
Language : En, Es, Fr & De

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Book Description :

This thesis describes investigations into unconventional pincer systems incorporating non-classical central donor groups. Direct reaction of 1,3-bis(diphenylphosphinomethyl)-2,3-dihydro-1H-1,3,2-benzodiazaborole (dppBH) with metal complexes and subsequent ligand manipulations have provided novel ruthenium and, for the first time, osmium boryl pincer complexes. The boryl complexes thus prepared have been observed to undergo various subsequent reactions involving the chloride and triphenylphosphine co-ligands to give new complexes. Further reactions of dppBH with complexes dichlorotris(triphenylphosphine)ruthenium(II) and -osmium(II) resulted in the first examples of sigma-borane pincer complexes, which represent intercepted intermediates in the B-H activation process, affording rare structural data for an osmium sigma-borane complex. The B-H bond of the ruthenium complex could be readily cleaved upon ligand manipulation, such as substitution of triphenylphosphine with the pi-acidic carbonyl and isocyanide ligands, which gave the disubstituted boryl complexes via spontaneous loss of HCl. Attempts to isolate a 1,8-diaminonaphthalene-based borane analogue of dppBH proved unsuccessful, though the compound 1,3 bis(diphenylphosphinomethyl)-2,3-dihydroperimidine (PhDHP) was obtained as a side-product in one case. Further investigations into this compound resulted in the development of a convenient one-pot synthesis, which could be extended to the cyclohexyl analogue 1,3 bis(dicyclohexylphosphinomethyl)-2,3-dihydroperimidine (CyDHP). These compounds were observed to react with various platinum group metal complexes to give novel N-heterocyclic carbene (NHC) pincer complexes via double geminal C-H activation of the central methylene group, providing the first examples of perimidine-based NHC inclusion as the central equatorial group of a pincer system. Reactions of dihydroperimidines with group 8 complexes dichlorotris(triphenylphosphine)ruthenium(II) and -osmium(II) have thus provided the novel pincer NHC complexes. However, reactions of PhDHP with dichlorotris(triphenylphosphine)ruthenium and CyDHP with less electron-rich ruthenium precursors instead gave asymmetric PNP coordinated complexes, in which C-H activation had not occurred, though this could be induced thermally in one case. Reactions of PhDHP and CyDHP with chlorotris(triphenylphosphine)rhodium(I) gave 16-electron chloro rhodium(I) NHC pincer complexes, and their reactivity was investigated via co-ligand manipulations and a preliminary catalytic study. The latter revealed that, while this complex was not particularly efficient for most of the reactions investigated, in some cases simple modifications of the co-ligands could substantially improve catalytic activity. Reactions of the pro-ligands with iridium precursors instead favoured the formation of coordinatively saturated complexes. The reaction of CyDHP with chlorobis(cyclooctene)iridium(I) dimer resulted in a dihydrido chloro iridium(III) NHC pincer complex, while reaction with chlorocarbonylbis(triphenylphosphine)iridium(I) instead afforded a sigma perimidinyl hydrido complex, resulting from oxidative addition of only one C-H bond to the metal centre. This was subsequently shown to readily form an NHC complex upon hydride abstraction. It became apparent that, upon reaction of the dihydroperimidine pro-ligands with metal complexes, carbene formation occurs more readily for electron-rich systems, otherwise resulting in either single or no C-H activation. These observations have provided some insight into the mechanism of NHC formation via chelate-assisted C-H activation of these precursors.

Photoluminescent Materials and Electroluminescent Devices

Photoluminescent Materials and Electroluminescent Devices Book
Author : Nicola Armaroli,Henk J. Bolink
Publisher : Springer
Release : 2017-05-25
ISBN : 3319593048
Language : En, Es, Fr & De

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Book Description :

The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.

Ligand Design in Metal Chemistry

Ligand Design in Metal Chemistry Book
Author : Mark Stradiotto,Rylan J. Lundgren
Publisher : John Wiley & Sons
Release : 2016-09-01
ISBN : 1118839811
Language : En, Es, Fr & De

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Book Description :

The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.

Homogeneous Hydrogenation

Homogeneous Hydrogenation Book
Author : P.A. Chaloner,M.A. Esteruelas,Ferenc Joó,L.A. Oro
Publisher : Springer Science & Business Media
Release : 2013-11-11
ISBN : 9401717915
Language : En, Es, Fr & De

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Book Description :

Homogeneous hydrogenation is one of the most thoroughly studied fields of homogeneous catalysis. The results of these studies have proved to be most important for an understanding of the underlying principles of the activation of small molecules by transition metal complexes. During the past three decades homogeneous hydrogenation has found widespread application in organic chemistry, including the production of important pharmaceuticals, especially where a sophisticated degree of selectivity is required. This volume presents a general account of the main principles and applications of homogeneous hydrogenation by transition metal complexes. Special attention is devoted to the mechanisms by which these processes occur, and the role of the recently discovered complexes of molecular hydrogen is described. Sources of hydrogen, other than H2, are also considered (transfer hydrogenation). The latest achievements in highly stereoselective hydrogenations have made possible many new applications in organic synthesis. These applications are documented by giving details of the reduction of important unsaturated substrates (alkenes, alkynes, aldehydes and ketones, nitrocompounds, etc.). Hydrogenation in biphasic and phase transfer catalyzed systems is also described. Finally, a discussion of the biochemical routes of H2 activation highlights the similarities and differences in performing hydrogenation in both natural and synthetic systems. For researchers working in the fields of homogeneous catalysis, especially in areas such as pharmaceuticals, plastics and fine chemicals.

Activation and Functionalization of C H Bonds

Activation and Functionalization of C H Bonds Book
Author : Karen I. Goldberg,Alan S. Goldman,American Chemical Society. Division of Inorganic Chemistry
Publisher : Amer Chemical Society
Release : 2004
ISBN : 9780841238497
Language : En, Es, Fr & De

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Book Description :

Activation and Functionalization of C-H Bonds explores recent developments in the reaction chemistry of solution-phase transition-metal based systems with simple hydrocarbons and with more complex organic molecules. More than 20 internationally leading research groups contributed to this volume, and their chapters cover such topics as fundamental theoretical and mechanistic studies of C-H bond activation by metal complexes, catalytic systems for alkane functionalization, and new applications in synthetic organic chemistry. An introductory chapter offers an overview of stoichiometric and catalytic reactions of C-H bonds with transition metal complexes. The C-H bond is the most widespread linkage in organic chemistry, present in virtually every organic molecule. Unfortunately, C-H bonds are famously resistant to selective chemical transformations. The development of methods for their selective transformations has enormous potential value in fields ranging from the chemistry of fuels (for example, the conversion of methane to methanol) to the synthesis of the most complex organic molecules.

Catalysis with Earth abundant Elements

Catalysis with Earth abundant Elements Book
Author : Uwe Schneider,Stephen Thomas
Publisher : Royal Society of Chemistry
Release : 2020-10-30
ISBN : 178801118X
Language : En, Es, Fr & De

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Book Description :

Considering the limited resources of our planet, earth-abundant elements will have to be explored increasingly in the future. This book highlights the uses of the most earth-abundant elements in catalysis and will be of interest to graduates, academic researchers and practitioners in catalysis.

Synthesis Reactivity and Catalytic Applications of Ruthenium and Palladium Complexes Supported by New Pincer Ligands

Synthesis  Reactivity  and Catalytic Applications of Ruthenium and Palladium Complexes Supported by New Pincer Ligands Book
Author : Morgan C. MacInnis,Dalhousie University. Department of Chemistry
Publisher : Unknown
Release : 2011
ISBN : 0987650XXX
Language : En, Es, Fr & De

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Book Description :

ABSTRACT continued: These transfer hydrogenation studies are among the first catalytic studies of silyl-pincer complexes and establish [R-PSiP]M species as viable candidates for catalysis. The synthesis and reactivity of 4- and 5-coordinate RuII complexes featuring the [Cy-PSiP] ligand were explored. Reaction of [Cy-PSiP]H with [(p-cymene)RuCl2]2 in the presence of NEt3 and PCy3 resulted in the formation of ([Cy-PSiP]RuCl)2, which serves as a precursor to a series of unprecedented 4-coordinate, formally 14-electron [Cy-PSiP]RuX (X = NHAr, N(SiMe3)2, OtBu) complexes that feature an unusual trigonal pyramidal geometry at Ru. The reactivity of these novel diamagnetic complexes is described, including the reaction of [Cy-PSiP]RuOtBu with amine-boranes resulting in the formation of rare bis(?-BH) complexes. Computational studies confirmed the key role of the strongly ?-donating silyl group of the Cy-PSiP ligand in facilitating the synthesis of such low-coordinate Ru species and enforcing the unusual trigonal pyramidal geometry. The mechanism of ammonia-borane activation was also examined computationally. Lastly, the synthesis and structural characterization of PdII complexes supported by the pincer-like bis(amino)phosphido ligand [?3-(2-Me2NC6H4)2P]- ([NPN]) is described. Examples of ?1-, ?2-, and ?3-NPN coordination to Pd are described, as is the catalytic activity of ([NPN]PdX)2 (X = Cl, OAc, OTf) complexes in the Heck olefin arylation reaction. In an effort to discourage the formation of phosphido-bridged dinuclear complexes, pre-coordination of the Lewis acid BPh3 to [NPN] was pursued. Upon reaction of [N(P?BPh3)N]K with [PdCl(C3H5)]2, the ?1-allyl complex [?3-N(P?BPh3)N]Pd(?1-C3H5) was isolated, which establishes the coordination of a Lewis acid to the phosphido donor of the [NPN] ligand as a viable strategy for encouraging the formation of mononuclear ?3-NPN complexes.

A Textbook of Inorganic Chemistry Volume 1

A Textbook of Inorganic Chemistry     Volume 1 Book
Author : Mandeep Dalal
Publisher : Dalal Institute
Release : 2017-01-01
ISBN : 8193872002
Language : En, Es, Fr & De

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Book Description :

An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory, dπ -pπ bonds, Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions, Trends in stepwise constants, Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand, Chelate effect and its thermodynamic origin, Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes, Mechanisms for ligand replacement reactions, Formation of complexes from aquo ions, Ligand displacement reactions in octahedral complexes- acid hydrolysis, Base hydrolysis, Racemization of tris chelate complexes, Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes, The trans effect, Theories of trans effect, Mechanism of electron transfer reactions – types; Outer sphere electron transfer mechanism and inner sphere electron transfer mechanism, Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory, Molecular orbital theory, octahedral, tetrahedral or square planar complexes, π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals, Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states), Calculation of Dq, B and β parameters, Effect of distortion on the d-orbital energy levels, Structural evidence from electronic spectrum, John-Tellar effect, Spectrochemical and nephalauxetic series, Charge transfer spectra, Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry, Guoy’s method for determination of magnetic susceptibility, Calculation of magnetic moments, Magnetic properties of free ions, Orbital contribution, effect of ligand-field, Application of magneto-chemistry in structure determination, Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes, Wade’s rules, Carboranes, Metal Carbonyl Clusters - Low Nuclearity Carbonyl Clusters, Total Electron Count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls, structure and bonding, Vibrational spectra of metal carbonyls for bonding and structure elucidation, Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.