Synthesis and Original Reactivity of Copper and Gold Complexes

1. Front Matter

   Pages i-xxvi

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2. General Introduction

   • Maximilian Joost

   Pages 1-4

3. Copper: σ-SiH Coordination to Cu(I)

   • Maximilian Joost

   Pages 5-29

4. Fundamental Elementary Steps in Gold Chemistry

   • Maximilian Joost

   Pages 31-81

5. Gold: Migratory Insertion at Au(I)

   • Maximilian Joost

   Pages 83-127

6. Gold: Oxidative Addition to Au(I)

   • Maximilian Joost

   Pages 129-193

7. General Conclusion and Perspective

   • Maximilian Joost

   Pages 195-198

8. Back Matter

   Pages 199-224

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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.

• Au complexes
• Coordination chemistry
• Copper
• Cu complexes
• Gold
• Gold catalysis
• Migratory insertion
• Oxidative addition
• σ-bond activation
• σ-bond coordination

• Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS, Toulouse, France

  Maximilian Joost

Maximilian Joost studied chemistry in Heidelberg (Germany) and Toulouse (France). He completed his M.Sc. (with Dr. G. Alcaraz and Dr. S. Sabo-Etienne) at the Université de Toulouse in 2011. He then joined the group of Dr. D. Bourissou and obtained a Ph.D. degree from the same university in 2014. His Ph.D. studies – which are presented in this book – revolved around new aspects regarding the coordination chemistry of copper and gold.

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