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This book presents an in-depth study into the utility of -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 -bond metathesis allows a novel hydrogen release from
silanes.
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.
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