January 20, 2021

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The Chemistry of Pincer Compounds

The Chemistry of Pincer Compounds
Author : David Morales-Morales,Craig G.M. Jensen
Publisher : Elsevier
Release Date : 2011-08-11
Category : Science
Total pages :466
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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

The Privileged Pincer-Metal Platform: Coordination Chemistry & Applications

The Privileged Pincer-Metal Platform: Coordination Chemistry & Applications
Author : Gerard van Koten,Robert A Gossage
Publisher : Springer
Release Date : 2015-08-27
Category : Science
Total pages :374
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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.

Organometallic Pincer Chemistry

Organometallic Pincer Chemistry
Author : Gerard van Koten,David Milstein
Publisher : Springer
Release Date : 2012-09-17
Category : Science
Total pages :356
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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.

Pincer and Pincer-Type Complexes

Pincer and Pincer-Type Complexes
Author : Kálmán J. Szabó,Ola F. Wendt
Publisher : John Wiley & Sons
Release Date : 2014-06-10
Category : Science
Total pages :320
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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.

Pincer Compounds

Pincer Compounds
Author : David Morales-Morales
Publisher : Elsevier
Release Date : 2018-04-11
Category : Science
Total pages :754
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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

Synthesis and Reactivity of Late Transition Metal Pincer Complexes

Synthesis and Reactivity of Late Transition Metal Pincer Complexes
Author : Karena A. Smoll
Publisher : Unknown
Release Date : 2018
Category :
Total pages :157
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Pincer Compounds

Pincer Compounds
Author : David Morales-Morales
Publisher : Elsevier
Release Date : 2018-04-11
Category : Science
Total pages :754
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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

Organotransition Metal Chemistry: From Bonding to Catalysis

Organotransition Metal Chemistry: From Bonding to Catalysis
Author : John F. Hartwig
Publisher : Univ Science Books
Release Date : 2010-02-10
Category : Science
Total pages :1127
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Based on Collman et al.'s best-selling classic book, Principles and Applications of Organotransition Metal Chemistry, Hartwig's text consists of new or thoroughly updated and restructured chapters and provides an in-depth view into mechanism, reaction scope, and applications. It covers the most important developments in the field over the last twenty years with great clarity with a selective, but thorough and authoritative coverage of the fundamentals of organometallic chemistry, the elementary reactions of these complexes, and many catalytic processes occurring through organometallic intermediates, making this the Organotransition Metal Chemistry text for a new generation of scientists.

Advances in Organometallic Chemistry

Advances in Organometallic Chemistry
Author : Pedro J. Perez
Publisher : Academic Press
Release Date : 2020-03-03
Category : Science
Total pages :314
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Advances in Organometallic Chemistry, Volume 73, the latest release in this longstanding serial, is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. It is ideal for a wide range of researchers involved in organometallic chemistry, including synthetic protocols, mechanistic studies and practical applications. Specific chapters in this new release include Metal carbonyl promoted multicomponent coupling of alkyne for synthesis of heterocyclic compounds, Group 10 metal(0) complexes stabilized by phosphorus and carbon donor ligands, Synthesis of Nitrogen-containing Molecules via Transition Metal-Catalyzed Reactions on Isoxazoles, Anthraniils and Benzoisoxazoles, and more. Contains contributions from leading authorities in the field of organometallic chemistry Covers topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more Informs and updates readers on the latest developments in the field Carefully edited to provide easy-to-read material

Synthesis of Pincer-type NHC Ligands with Phosphorus Functionalities and Their Ag(I), Cu(I) and Ir(I/III) Organometallic Complexes

Synthesis of Pincer-type NHC Ligands with Phosphorus Functionalities and Their Ag(I), Cu(I) and Ir(I/III) Organometallic Complexes
Author : Xianghao Liu
Publisher : Unknown
Release Date : 2011
Category :
Total pages :166
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Although the first metal complexes with the cyclometalated PCP pincer ligands (Figure 1a) were reported about 30 years ago, it is still a hot and fast developing topic covering all aspects of chemistry: mechanistic, structural, catalytic, synthetic, theoretical, and coordination studies. Pincer-based metal complexes possess a unique balance of stability and reactivity that can be controlled by systematic ligand modifications and variation of the metal centre.Numerous metal complexes with related pincer-type NHC ligands (Figure 1b) have been reported and well characterized (with e.g. CCC or CNC donor sets). Largely because the NHC ligands have a lesser tendency to dissociate from the metal centre than phosphines, their complexes exhibit advantages over phosphine metal complexes, such as improved air and thermal stability, which are highly desirable in e.g. organometallic chemistry and homogeneous catalysis. The aim of this thesis was to design and synthesize partial/full NHC analogues to the PCP framework, which may result in CCP, CCOP and CCC pincer ligands. Among the transition metals, silver and iridium are at the focus of our work because (i) NHC ligands bound to Ag(I) can generally be transferred to another metal and (ii) Ir complexes are good candidates for the challenging Csp3-H bond activation and hydrogen transfer reactions. Three different types of ligand precursors have been successfully synthesized: 1) bis-imidazolium salts with a methylene bridge connecting the aromatic ring to each of the two imidazole rings; 2) hybrid phosphino-imidazolium salts with a methylene bridge connecting the aromatic ring to the imidazole ring and to the phosphine group; 3) hybrid phosphinito-imidazolium salts where the corresponding oxygen and nitrogen atoms, respectively, are directly connected to the aromatic ring. The corresponding metal carbene complexes were prepared in situ from these imidazolium precursors in the presence of the weak base Cs2CO3 and isolated.The bis-NHC ligandTwo mutually meta positions of the aromatic ring were blocked with methyl groups to avoid possible ortho-C-H activation on the ring so that only pincer-type complexes would form if metalation was to occur on the aromatic ring. The bromides in the imidazolium dibromide salt were replaced with non-coordinating counterions PF6 to suppress their high hygroscopic character.An initial coordination chemistry study was performed by reaction of 1 with Ag2O as a weak base. However, owing to possible H-bonding between the NCHN units and a fluorine atom of PF6, Ag2O was not able to deprotonate the imidazolium to generate the silver NHC complex. However, the corresponding Cu(I) complex was obtained by treating the imidazolium salt with [Cu(NCMe)4]PF6 and Cs2CO3 in MeCN at 60 _C. Surprisingly, a transmetalation reaction between 4 and AgOTF afforded the desired Ag(I) complex 5. This reaction is particularly noteworthy since carbene transmetalation reactions always feature the opposite reaction (from Ag to Cu).The short distances observed by X-ray diffraction for 4 and 5 between the metal and the aromatic rings led us to examine whether these d10 metal centers are better described as T/Y-shaped tri-coordinated or linearly di-coordinated, and the results of detailed DFT calculations suggested the absence of a chemical bond between the Cu(I) or Ag(I) center and parts of the aromatic ring. The proximity observed experimentally between the aromatic carbon and the metals thus results from the combined effects of a chelating ligand structure and the metal preferred coordination geometry.In the cases of iridium complexes, the nature of the metal precursors played an important role. In complex 7, the cod ligand was preferably chelated to the Ir center and the two bridging CNHC^CH^CNHC ligands connect the Ir(I) centres in such a way that each metal is bonded to two mutually cis carbene donors, resulting in a dicationic 20-membered dimetallacycle. While cyclooctene (coe) is more labile than 1,5-cyclooctadiene (cod), it was easily replaced by the solvent molecule MeCN which coordinates to the Ir center through its nitrogen in complex 6. The requirement for shorter reacting times (compared with the reaction using [Ir(cod)(μ-Cl)]2) also showed the higher lability of the complex resulting from a more weakly bound coe ligand compared to cod. Unlike the situation found in the figure-of-eight complex 7, the aromatic ring was metalated, resulting in the formation of an Ir-C and an Ir-H bond. Mixtures of solvents were used to increase the solubility of the ligand (soluble in MeCN) and [Ir(coe)2(μ-Cl)]2 (soluble in THF). It is worth mentioning that MeCN seemed to have stabilized the pincer-type Ir(III) hydride because when bis-imidazolium dibromide, which is soluble in THF, was treated under the same conditions but in the absence of MeCN, only decomposition of the Ir precursor was observed.Hybrid phosphino-NHC ligandIn order to limit possible problems associated with the sensitivity of uncoordinated phosphine groups, we introduced the P-donor moiety in the final step of the preparation. Diethyl ether was used as the solvent in the first step to precipitate the mono-substituted derivative, thus preventing further substitution eventhough 1,3-bis(chloromethyl)benzene was present in large excess. [...].

Enantioselective Organocatalysis

Enantioselective Organocatalysis
Author : Peter I. Dalko
Publisher : John Wiley & Sons
Release Date : 2007-04-17
Category : Science
Total pages :536
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In this reference leaders at the forefront of research provide an insight into one of the hottest topics in organic synthesis, focusing on the most important enantioselective reactions. Clearly structured, each entry begins with a concise introduction, including a mechanistic discussion of the reaction, followed by preparative guidelines for newcomers, such as carefully selected working procedures with critical notes for bench chemists, rules of thumb and tips and tricks.

The Organometallic Chemistry of the Transition Metals

The Organometallic Chemistry of the Transition Metals
Author : Robert H. Crabtree
Publisher : John Wiley & Sons
Release Date : 2011-09-20
Category : Science
Total pages :520
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Bifunctional Molecular Catalysis

Bifunctional Molecular Catalysis
Author : Takao Ikariya,Masakatsu Shibasaki
Publisher : Springer
Release Date : 2011-06-24
Category : Science
Total pages :212
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Masakatsu Shibasaki, Motomu Kanai, Shigeki Matsunaga, and Naoya Kumagai: Multimetallic Multifunctional Catalysts for Asymmetric Reactions.- Takao Ikariya: Bifunctional transition metal-based molecular catalysts for asymmetric syntheses.- Chidambaram Gunanathan and David Milstein: Bond Activation by Metal-Ligand Cooperation: Design of ”Green” Catalytic Reactions Based on Aromatization-Dearomatization of Pincer Complexes.- Madeleine C. Warner, Charles P. Casey, and Jan-E. Bäckvall: Shvo’s Catalyst in Hydrogen Transfer Reactions.- Noritaka Mizuno, Keigo Kamata, and Kazuya Yamaguchi: Liquid-Phase Selective Oxidation by Multimetallic Active Sites of Polyoxometalate-Based Molecular Catalysts.- Pingfan Li and Hisashi Yamamoto: Bifunctional Acid Catalysts for Organic Synthesis.- Jun-ichi Ito, Hisao Nishiyama: Bifunctional Phebox Complexes for Asymmetric Catalysis.

Copper(I) Chemistry of Phosphines, Functionalized Phosphines and Phosphorus Heterocycles

Copper(I) Chemistry of Phosphines, Functionalized Phosphines and Phosphorus Heterocycles
Author : Maravanji S. Balakrishna
Publisher : Elsevier
Release Date : 2019-04-25
Category : Science
Total pages :442
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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

Non-Noble Metal Catalysis

Non-Noble Metal Catalysis
Author : Robertus J. M. Klein Gebbink,Marc-Etienne Moret
Publisher : Wiley-VCH
Release Date : 2019-05-07
Category : Technology & Engineering
Total pages :616
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An expert overview of current research, applications, and economic and environmental advantages The study and development of new homogeneous catalysts based on first-row metals (Mn, Fe, Co, Ni, and Cu) has grown significantly due to the economic and environmental advantages that non-noble metals present. Base metals offer reduced cost, greater supply, and lower toxicity levels than noble metals?enabling greater opportunity for scientific investigation and increased development of practical applications. Non-Noble Metal Catalysis provides an authoritative survey of the field, from fundamental concepts and computational methods to industrial applications and reaction classes. Recognized experts in organometallic chemistry and homogeneous catalysis, the authors present a comprehensive overview of the conceptual and practical aspects of non-noble metal catalysts. Examination of topics including non-innocent ligands, proton-coupled electron transfer, and multi-nuclear complexes provide essential background information, while areas such as kinetic lability and lifetimes of intermediates reflect current research and shifting trends in the field. This timely book demonstrates the efficacy of base metal catalysts in the pharmaceutical, fine-chemical, and agrochemical industries, addressing both environmental and economic concerns. Providing essential conceptual and practical exploration, this valuable resource: -Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications -Highlights the multiple advantages of using non-noble metals in homogenous catalysis -Demonstrates how the availability of non-noble metal catalysis reduces costs and leads to immense savings for the chemical industry -Reveals how non-noble metal catalysis are more sustainable than noble metals such as palladium or platinum Non-Noble Metal Catalysis: Molecular Approaches and Reactions is an indispensable source of up-to-date information for catalytic chemists, organic chemists, industrial chemists, organometallic chemists, and those seeking to broaden their knowledge of catalytic chemistry.