Relativistic Effects in Homogeneous Gold Catalysis

Relativistic Effects in Homogeneous Gold Catalysis

2007-03-22 | David J. Gorin, F. Dean Toste
The article "Relativistic Effects in Homogeneous Gold Catalysis" by David J. Gorin and F. Dean Toste explores the unique reactivity and catalytic properties of gold(I) complexes, particularly cationic phosphine-gold(I) complexes. These complexes have gained attention for their versatility and selectivity in various synthetic transformations. The authors highlight the importance of relativistic effects in understanding the electronic structure and reactivity of gold(I) species, which are characterized by a contracted 6s orbital and expanded 5d orbitals. These effects contribute to the strong Lewis acidity and unique reactivity of gold(I) catalysts, enabling them to activate alkynes and other π-systems for nucleophilic addition reactions. The review also discusses the role of ligand effects and the potential for backbonding in gold(I) complexes, which can lead to the formation of carbenoid intermediates. Experimental and computational studies are presented to support these theoretical insights, providing a comprehensive overview of the current understanding of homogeneous gold catalysis and its applications in developing new synthetic methodologies.The article "Relativistic Effects in Homogeneous Gold Catalysis" by David J. Gorin and F. Dean Toste explores the unique reactivity and catalytic properties of gold(I) complexes, particularly cationic phosphine-gold(I) complexes. These complexes have gained attention for their versatility and selectivity in various synthetic transformations. The authors highlight the importance of relativistic effects in understanding the electronic structure and reactivity of gold(I) species, which are characterized by a contracted 6s orbital and expanded 5d orbitals. These effects contribute to the strong Lewis acidity and unique reactivity of gold(I) catalysts, enabling them to activate alkynes and other π-systems for nucleophilic addition reactions. The review also discusses the role of ligand effects and the potential for backbonding in gold(I) complexes, which can lead to the formation of carbenoid intermediates. Experimental and computational studies are presented to support these theoretical insights, providing a comprehensive overview of the current understanding of homogeneous gold catalysis and its applications in developing new synthetic methodologies.
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[slides and audio] Relativistic effects in homogeneous gold catalysis