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Book Synthesis and Original Reactivity of Copper and Gold Complexes

Download or read book Synthesis and Original Reactivity of Copper and Gold Complexes written by Maximilian Joost and published by Springer. This book was released on 2015-06-13 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of σ-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first σ-SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into σ-bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of σ-SiSi, σ-CC and σ-CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of σ-CC and σ-CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

Book Synthesis and Reactivity of Copper i  Amidinate Complexes

Download or read book Synthesis and Reactivity of Copper i Amidinate Complexes written by Andrew C. Lane and published by . This book was released on 2015 with total page 87 pages. Available in PDF, EPUB and Kindle. Book excerpt: Group 11 transition metals are used daily throughout our bodies and as additives in many common products. One biological function of copper, a group 11 metal, is its use in the Cu A site of cytochrome c oxidase, an enzyme found in the last step of cellular respiration. To model this active site, three formamidinate ligands have been examined: 2,6-dimethylphenyl, 2,6- diisopropylphenyl, and 2,4,6-trimethylphenyl. The synthesis and structural characterization of these dinuclear Cu(I) complexes is described as well as their redox chemistry with I 2 to afford complexes of mixed-valence which is the normal resting state of the Cu A site. Using EPR spectroscopy and DFT calculations on the iodine oxidized products, different electronic structures base d on the formamidinate was found. Additionally, insertion of CS 2 into the copper-nitrogen bonds of the copper(I) formamidinate complexes produces tetra- and hexanuclear clusters based on the steric properties of the ligand

Book Synthesis and Reactivity of Copper I  and Iron II  Carboxylate bridged Dimetallic Complexes

Download or read book Synthesis and Reactivity of Copper I and Iron II Carboxylate bridged Dimetallic Complexes written by Daniel David LeCloux and published by . This book was released on 1998 with total page 568 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands

Download or read book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands

Download or read book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands written by Elizabeth D. Blue and published by . This book was released on 2006 with total page 194 pages. Available in PDF, EPUB and Kindle. Book excerpt: Presented herein are the isolation and characterization of a number of new copper(I) halide complexes and the first two examples of monomeric copper(I) amido complexes, (dtbpe)Cu(NHPh) and (IPr)Cu(NHPh). These Cu(I) anilido complexes have been shown to be more nucleophilic than a related Ru(II) anilido complex in reactivity studies with bromoethane, and reveal increasing nucleophilicity in the order (SIPr)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh). (IPr)Cu(NHPh) is thermodynamically favored over (IPr)Cu(Ph)/NH2Ph or [(IPr)Cu(mu-H)]2/NH2Ph, respectively. Computational studies are consistent with the observed reactivity and indicate strong Cu-N bonds with nucleophilic amido nitrogen.

Book Synthesis and Original Reactivity of Copper and Gold Complexes

Download or read book Synthesis and Original Reactivity of Copper and Gold Complexes written by Maximilian Joost and published by . This book was released on 2014 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The present work is a study concerning the coordination chemistry and reactivity of copper and gold complexes. Of particular interest was the elucidation of (i) the metal-mediated activation of s-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but elusive for copper and gold. The first part of this manuscript is dedicated to the study of the coordination of s-SiH bonds to copper. By means of a chelate assistance approach, we synthesized copper complexes employing diphosphino-hydrosilane ligands (R2P(o-C6H4))2Si(R')H. This study allowed for the identification of a weak ?2-SiH coordination to copper that has been evidenced by experimental (NMR, IR, XRD) and computational (geometry optimization, NBO analysis) means. The s-SiH coordination is essentially dominated by donation of electron density from the hydrosilane moiety to copper, without significant backdonation. In the second part, we investigated the reactivity of silylgold(I) complexes towards unsaturated organic molecules. We showed that these complexes react with alkynes and allenes to yield (Beta-silyl)vinylgold complexes via migratory syn insertion into the gold-silicon bond. A mechanistic proposal consisting of a 2-step coordination insertion process was established for this transformation by means of a kinetic and computational study. In the third part, the intermolecular oxidative addition of s-SiSi, s-CC and s-CX (X=halogen) bonds with molecular gold(I) complexes was studied in detail. We showed that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. Disilanes add to cationic monophosphine gold(I) complexes. However, the corresponding bis(silyl)gold(III) products are highly unstable. The use of bis(phosphine) gold(I) complexes, featuring a bidentate ligand with a small bite-angle, allowed for the first time for the oxidative addition of s-CC and s-CX bonds at gold(I) and proved key for the stabilization of the corresponding gold(III) products that were characterized by spectroscopic and structural means. These results shed light on an unexpected reactivity pattern of gold complexes and may be an entry point to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

Book Synthesis and Copper  I  Coordination Chemistry of Tris mercaptoimidazolyl  Mesitylenes

Download or read book Synthesis and Copper I Coordination Chemistry of Tris mercaptoimidazolyl Mesitylenes written by Javier Ulises Pacheco and published by . This book was released on 2010 with total page 132 pages. Available in PDF, EPUB and Kindle. Book excerpt: To study the functional properties of copper proteins several copper(I) complexes have been used for modeling biological sites. A new family of neutral tris(thione) ligands, the tris(mercaptoimidazolyl)mesitylenes R3TmmesMe (R = H, Me, Et) have been synthesized. The ligand system presented good solubility in organic solvents and stability. The corresponding copper(I) complexes were synthesized and characterized in the search for potential synthetic analogues of the metal center in copper enzymes. The effect of the alkyl substituent on the aromatic ring showed to have an unexpected effect on the reactivity of these ligands towards copper(I) ions. Reactivity studies of these complexes were done with different donor ligands like thiolates, tetramethylthiourea, triphenylphosphine and pyridine. Reactions with silver(I) and cobalt(II) were also tried to study the relationship of the ligand system with biologically relevant metals. The data and structures obtained is compared and discussed in the context of obtaining a mononuclear complex.

Book Synthesis and Reactivity of Copper I   Copper II   Platinum II  and Platinum IV  Complexes with Non dative Heteroatomic Ligands

Download or read book Synthesis and Reactivity of Copper I Copper II Platinum II and Platinum IV Complexes with Non dative Heteroatomic Ligands written by Colleen Munro-Leighton and published by . This book was released on 2008 with total page 252 pages. Available in PDF, EPUB and Kindle. Book excerpt: Keywords: hydroamination, copper(I), platinum(IV), platinum(II), hydroalkoxylation, hydrothiolation, C-H activation.

Book Journal

    Book Details:
  • Author : American Chemical Society
  • Publisher :
  • Release : 2001
  • ISBN :
  • Pages : 1320 pages

Download or read book Journal written by American Chemical Society and published by . This book was released on 2001 with total page 1320 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Direct Synthesis of Metal Complexes

Download or read book Direct Synthesis of Metal Complexes written by B.I. Kharisov and published by Elsevier. This book was released on 2018-04-19 with total page 470 pages. Available in PDF, EPUB and Kindle. Book excerpt: Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn’t require organic solvents), with special attention paid to ‘greener’ methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water Includes experimental procedures, with examples of direct synthesis, at the end of each chapter

Book Highly Efficient OLEDs

Download or read book Highly Efficient OLEDs written by Hartmut Yersin and published by John Wiley & Sons. This book was released on 2019-01-04 with total page 604 pages. Available in PDF, EPUB and Kindle. Book excerpt: Dieses Fachbuch eines Pioniers in diesem schnell wachsenden Fachbereich fasst die jüngsten Erkenntnisse zur Optimierung von OLEDs zusammen. Die Theorie wird ausführlich beschrieben, ebenso verschiedene organische und anorganische emittierende Materialien, Display- und Lichtanwendungen.

Book Chemistry of Thioamides

    Book Details:
  • Author : Toshiaki Murai
  • Publisher : Springer
  • Release : 2020-08-14
  • ISBN : 9789811378300
  • Pages : 238 pages

Download or read book Chemistry of Thioamides written by Toshiaki Murai and published by Springer. This book was released on 2020-08-14 with total page 238 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book covers whole aspects of the sulfur isologues of amides. Starting from the synthetic methods of thioamides, a range of synthetic applications to the construction of carbon–sulfur and carbon–carbon bonds, to asymmetric reactions, to formation of heterocycles are described. Among the array of thiocarbonyl compounds, thioamides are readily handled in room temperature air. Some of their characteristic features are that the polarity of C=S bonds in thioamides is much smaller than C=O bonds in ordinary amides, that thioamides possess higher HOMO and lower LUMO when compared with those of ordinary amides, and that carbon atoms alpha to the C=S and nitrogen atoms in thioamides are more acidic than those in ordinary amides. Theoretical studies further disclose their features. Thioamides are also used as ligands to a wide variety of metals. Their unique photophysical properties and catalytic activities are described here. Characteristic features of biologically relevant thioamides, e.g., thiopeptides and related compounds, are the final focus of the book.

Book Catalytic Asymmetric Synthesis

Download or read book Catalytic Asymmetric Synthesis written by Takahiko Akiyama and published by John Wiley & Sons. This book was released on 2022-05-27 with total page 798 pages. Available in PDF, EPUB and Kindle. Book excerpt: Catalytic Asymmetric Synthesis Seminal text presenting detailed accounts of the most important catalytic asymmetric reactions known today This book covers the preparation of enantiomerically pure or enriched chemical compounds by use of chiral catalyst molecules. While reviewing the most important catalytic methods for asymmetric organic synthesis, this book highlights the most important and recent developments in catalytic asymmetric synthesis. Edited by two well-qualified experts, sample topics covered in the work include: Metal catalysis, organocatalysis, photoredox catalysis, enzyme catalysis C–H bond functionalization reactions Carbon–carbon bond formation reactions, carbon–halogen bond formation reactions, hydrogenations, polymerizations, flow reactions Axially chiral compounds Retaining the best of its predecessors but now thoroughly up to date with the important and recent developments in catalytic asymmetric synthesis, the 4th edition of Catalytic Asymmetric Synthesis serves as an excellent desktop reference and text for researchers and students, from upper-level undergraduates all the way to experienced professionals in industry or academia.

Book Side Reactions in Organic Synthesis

Download or read book Side Reactions in Organic Synthesis written by Florencio Zaragoza Dörwald and published by John Wiley & Sons. This book was released on 2006-03-06 with total page 389 pages. Available in PDF, EPUB and Kindle. Book excerpt: Most syntheses in the chemical research laboratory fail and usually require several attempts before proceeding satisfactorily. Failed syntheses are not only discouraging and frustrating, but also cost a lot of time and money. Many failures may, however, be avoided by understanding the structure-reactivity relationship of organic compounds. This textbook highlights the competing processes and limitations of the most important reactions used in organic synthesis. By allowing chemists to quickly recognize potential problems this book will help to improve their efficiency and success-rate. A must for every graduate student but also for every chemist in industry and academia. Contents: 1 Organic Synthesis: General Remarks 2 Stereoelectronic Effects and Reactivity 3 The Stability of Organic Compounds 4 Aliphatic Nucleophilic Substitutions: Problematic Electrophiles 5 The Alkylation of Carbanions 6 The Alkylation of Heteroatoms 7 The Acylation of Heteroatoms 8 Palladium-Catalyzed C-C Bond Formation 9 Cyclizations 10 Monofunctionalization of Symmetric Difunctional Substrates