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This book presents an in-depth study into the utility of s-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner. Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with s-bond metathesis allows a novel hydrogen release from silanes.
Sommario
Introduction.- Group 1-Group 2 Bimetallic Alkyls and Hydrides.- Silicon-nitrogen Dehydrocoupling.- Boron-nitrogen Dehydrocoupling.- Single Electron Transfer Steps in Group 2 Catalysis.- Summary.- Future Work.
Info autore
David received his first degree (MChem (Hons)) in Chemistry with Industrial Training) in 2011 from the University of Bath, Bath, UK. David remained at Bath to subsequently work on Group 2 chemistry in the laboratory of Professor Michael Hill and was awarded his PhD for this work in 2014. David then undertook a short postdoctoral appointment focussing on novel oligo- and polystannanes collaborating between Bath and Professor Roland Fischer at TU Graz, Austria. In 2015, David took up a Lindemann Postdoctoral Fellowship researching p-block mediated small molecule activation in the laboratory of Professor Philip Power at UC Davis, USA.
Riassunto
This book presents an in-depth study into the utility of σ-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner. Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with σ-bond metathesis allows a novel hydrogen release from silanes.
