Regioselective [2+2] and [4+2] cycloaddition reactivity in an asymmetric niobium(bisimido) moiety towards unsaturated organic molecules

The asymmetric bis-imido structure and the lability of the diethyl ether linkage in complex 1 provide a niobium complex that undergoes regioselective [4+2] cycloaddition reactions with an α,β-unsaturated ketone and cycloaddition reactions that involve bond formation to the MAD ligand (MonoAzabutaDie...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2015-01, Vol.51 (7), p.1278-1281
Main Authors: Obenhuber, A H, Gianetti, T L, Bergman, R G, Arnold, J
Format: Article
Language:English
Subjects:
Alkynes
Asymmetry
Bonding
Cycloaddition
Diethyl ether
Ligands
Mathematical analysis
Organic chemistry
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Summary:The asymmetric bis-imido structure and the lability of the diethyl ether linkage in complex 1 provide a niobium complex that undergoes regioselective [4+2] cycloaddition reactions with an α,β-unsaturated ketone and cycloaddition reactions that involve bond formation to the MAD ligand (MonoAzabutaDiene). DFT calculations have been used to support an initial azametallacyclobutene intermediate in the alkyne reaction.
ISSN:1359-7345
1364-548X
DOI:10.1039/c4cc07851a