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

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.

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.

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:

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:

Download or read book Synthesis and Reactivity of Bio Inspired Copper Complexes Supported by Non Traditional Ligands written by Aalo Kumar Gupta and published by . This book was released on 2011 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Reactivity of Copper I and Aluminium III Complexes of N heterocyclic Carbenes written by Michael Trose and published by . This book was released on 2017 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

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.

Download or read book Synthesis and Dioxygen Reactivity of Copper I Complexes of Sterically Encumbered Imidazole Ligands written by William E. Allen and published by . This book was released on 1995 with total page 246 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Copper Catalysis in Organic Synthesis written by Gopinathan Anilkumar and published by John Wiley & Sons. This book was released on 2020-12-07 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: The most current information on growing field of copper catalysis Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors—noted experts on the topic—provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C–H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions. Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions Presents the most significant developments in the area, including cross-coupling reactions, C–H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles Contains over 20 contributions from leaders in the field Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C–H activation, and applications in the total synthesis of natural products.

Download or read book Copper Catalyzed Asymmetric Synthesis written by Alexandre Alexakis and published by John Wiley & Sons. This book was released on 2013-12-30 with total page 467 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book reflects the increasing interest among the chemical synthetic community in the area of asymmetric copper-catalyzed reactions, and introduces readers to the latest, most significant developments in the field. The contents are organized according to reaction type and cover mechanistic and spectroscopic aspects as well as applications in the synthesis of natural products. A whole chapter is devoted to understanding how primary organometallics interact with copper to provide selective catalysts for allylic substitution and conjugate addition, both of which are treated in separate chapters. Another is devoted to the variety of substrates and experimental protocols, while an entire chapter covers the use on non-carbon nucleophiles. Other chapters deal with less-known reactions, such as carbometallation or the additions to imines and related systems, while the more established reactions cyclopropanation and aziridination as well as the use of copper (II) Lewis acids are warranted their own special chapters. Two further chapters concern the processes involved, as determined by mechanistic studies. Finally, a whole chapter is devoted to the synthetic applications. This is essential reading for researchers at academic institutions and professionals at pharmaceutical or agrochemical companies.

Download or read book Synthesis Structure and Oxygenation Reactivity of Copper Complexes Supported by Monodentate Arylamido Ligands written by Yat Kit Chen and published by . This book was released on 2013 with total page 384 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter one gives an overview on the chemistry of metal amides. A brief introduction to copper-dioxygen chemistry is also presented.

Download or read book The Synthesis Characterization and Reactivity of Copper Nitrosyl Complexes with Sterically Hindered Tris pyrazolyl hydroborate Ligands written by Susan Marie Carrier and published by . This book was released on 1995 with total page 336 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Studies on the Synthesis and Reactivity of Copper Thiolate and Thiomide Complexes written by A. G. Bingham and published by . This book was released on 1984 with total page 466 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Using Insertion Chemistry to Synthesize New Coordination Environments for Organoactinide Complexes to Examine Structure Bonding and Reactivity written by Justin R. Walensky and published by . This book was released on 2009 with total page 235 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation uses insertion chemistry to create new coordination environments for actinide complexes and examines their subsequent reactivity. Since actinides play such a prominent role in nuclear processes and their disposal is an environmental issue, the study of their structure, reactivity, and coordination chemistry is of interest. This work has resulted in the isolation of new organoactinide complexes, new reactivity patterns, and new coordination modes of common substrates not seen before in f element chemistry. Chapter 1 gives details about the synthesis of mono(pentamethycyclopentadienyl) divalent lanthanide complexes, (C5Me5)Ln(BPh4), and their unusual structural arrangements that were observed in their crystal structures. The reductive and displacement reactivity of the samarium and ytterbium complexes is also described. In Chapter 2, the utility of cationic complexes in making sterically crowded uranium complexes is described with the synthesis of (C5Me5)2(C5Me4H)UMe. This complex does not have reductive reactivity like (C5Me5)3UMe and not all the methyl groups are displaced from the cyclopentadienyl ring plane equally. The synthesis of (C5Me5)2UMe[CH(SiMe3)2], the first mixed-alkyl actinide metallocene complex, is also shown. Chapter 3 starts a series of chapters on the metallocene amidinate moiety, {(C5Me5)2[iPrNC(Me)NiPr]}3- from insertion of iPrN=C=NiPr into one methyl group of (C5Me5)2AnMe2 to produce, (C5Me5)2[iPrNC(Me)NiPr]AnMe, An = Th, U. In addition, insertion of AdN3, Ad = adamantyl, into (C5Me5)2AnMe2 produces the metallocene triazenido complex, (C5Me5)2[(Ad)NNN(Me)]AnMe. Cationic metallocene amidinate complexes can be made by the abstraction of the methyl group in (C5Me5)2[iPrNC(Me)NiPr]AnMe with BPh3 to produce {(C5Me5)2[iPrNC(Me)NiPr]An}{BPh3Me}, An = Th, U. Reaction of KC5Me5 with each actinide complex produces the thorium "tuck-in" complex, (C5Me5)(C5Me4CH2)[iPrNC(Me)NiPr]Th, by C-H bond activation, and the trivalent uranium complex, (C5Me5)2[iPrNC(Me)NiPr]U, by reduction. This is detailed in Chapter 4. The comparative reactivity of (C5Me5)2[iPrNC(Me)NiPr]UMe and (C5Me5)2[(Ad)NNN(Me)]UMe is described in chapter 5. The abstraction of the methyl group by silver and copper salts to produce the corresponding halide and triflate complexes is demonstrated. This is the first time that copper salts have been shown to have this type of reactivity. Interestingly, the reaction of the amidinate complex with LiCH2SiMe3 leads to the trivalent species, (C5Me5)2[iPrNC(Me)NiPr]U, through reduction, but the reaction with the triazenido complex with yields the corresponding alkyl complex, (C5Me5)2[(Ad)NNN(Me)]U(CH2SiMe3). Further, the reaction of (C5Me5)2[iPrNC(Me)NiPr]UMe with the bulky alcohol, HOC6H2iPr2-2,6-4-Me, produces an unusual outer sphere aryloxide complex, {(C5Me5)2[iPrNC(Me)NiPr]U}{OAr}. In chapter 6, the reductive chemistry of (C5Me5)2[iPrNC(Me)NiPr]U is examined. Aryl sulfides, copper salts, and TlC5H5 prove to react with the trivalent complex, but this complex is far much less reactive than other trivalent uranium complexes. In chapter 7, the synthesis of a rare trivalent thorium complex, (C5Me5)2[iPrNC(Me)NiPr]Th is reported. In addition, the electronic structure and bonding of trivalent metallocene amidinate complexes, (C5Me5)2[iPrNC(Me)NiPr]An, An=Th, Pa, U, Np, Pu, Am, is described. Chapter 8 looks at the insertion chemistry of (C5Me5)2U(C & 881CPh)2 with the unsaturated substrates, CO2, PhNCO, Me3CC & 881N, and Me3CN & 881C. Insertion chemistry is one of the steps in the mechanism of catalytic and cascade reactions with the dialkynyl complex. Appendix A describes a new way of abstracting a methyl group of (C5Me5)2ThMe2 with 2,6-tetramethylpiperdine oxide (TEMPO) to produce, (C5Me5)2[C5H6NMe4-2,6-O]ThMe. The methyl group can also be abstracted with CuBr to produce the corresponding bromide. In addition, the reaction of (C5Me5)2Eu with benzaldehyde azine, PhCH=NN=CHPh, is described. The dark purple product, (C5Me5)2Eu(C14H12N2), is still a divalent europium with a coordinating ligand. Moreover, the lanthanide metallocene amidinate complex, (C5Me5)2[iPrNC(Me)NiPr]Ce, was crystallographically characterized and is discussed.

Download or read book Advances in Organometallic Chemistry written by Anthony F. Hill and published by Academic Press. This book was released on 2013-09-11 with total page 484 pages. Available in PDF, EPUB and Kindle. Book excerpt: Almost all branches of chemistry and material science now interface with organometallic chemistry--the study of compounds containing carbon-metal bonds. This widely acclaimed serial contains authoritative reviews that address all aspects of organometallic chemistry, a field that has expanded enormously since the publication of Volume 1 in 1964. Informs and updates on all the latest developments in the field Contributions from leading authorities and industry experts

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.