Synthesis, Characterization, and Reactivity of Monomeric Copper(I) Complexes Possessing Pi-donor Ligands PDF Download
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Author: Samuel A. Delp
Publisher:
ISBN:
Category :
Languages : en
Pages : 185
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Author: Samuel A. Delp
Publisher:
ISBN:
Category :
Languages : en
Pages : 185
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Author: Susan Marie Carrier
Publisher:
ISBN:
Category :
Languages : en
Pages : 336
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Author: Maximilian Joost
Publisher: Springer
ISBN: 3319186906
Category : Science
Languages : en
Pages : 244
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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.
Author: Adam Ruddy
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author:
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Category :
Languages : en
Pages :
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Author: Björn Gustafsson
Publisher:
ISBN: 9789172915152
Category :
Languages : en
Pages :
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Author: Mikael Håkansson
Publisher:
ISBN: 9789170325083
Category : Alkenes
Languages : en
Pages : 61
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Author: Stacy A. Williams
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Author: R. Bryan Scott Klassen
Publisher:
ISBN:
Category :
Languages : en
Pages : 442
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Author: Andrew C. Lane
Publisher:
ISBN:
Category :
Languages : en
Pages : 87
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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
