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Group 2 promoted hydrogen release from NMe2H.BH3: intermediates and catalysis
David J Liptrot1, Michael S Hill, Mary F Mahon
1Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY UK.
Group 2 metal complexes of magnesium and calcium catalyze the dehydrocoupling of dimethylamine-borane. This reaction forms cyclic products and metal hydride species via novel delta-hydride elimination.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Boron Chemistry
Background:
- Group 2 metal complexes are increasingly explored as catalysts.
- Amine-borane dehydrocoupling is a key reaction for B-N bond formation.
Purpose of the Study:
- To investigate the catalytic activity of Group 2 metal complexes in amine-borane dehydrocoupling.
- To elucidate the mechanism of this catalytic transformation.
Main Methods:
- Synthesis of magnesium and calcium alkyl and amide complexes.
- Catalytic dehydrocoupling reactions with dimethylamine-borane.
- Spectroscopic and crystallographic characterization of intermediates and products.
Main Results:
- Magnesium and calcium complexes effectively catalyze the dehydrocoupling of dimethylamine-borane.
- Formation of a novel anionic B-N species coordinated to magnesium.
- Thermolysis yields cyclic products and magnesium hydride species via delta-hydride elimination.
- Calcium complexes show similar reactivity but are less reactive than magnesium counterparts.
Conclusions:
- A mechanism involving H2B=NMe2 insertion into M-N bonds and subsequent hydride elimination is proposed.
- Reactivity differences between Mg and Ca are attributed to charge density and polarization.
- This study expands the scope of Group 2 metal catalysis in B-N bond formation.
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