New Boron Complexes with Unpredicted Reactivity

  • Author: ChemViews
  • Published Date: 17 August 2011
  • Source / Publisher: Angewandte Chemie International Edition/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: New Boron Complexes with Unpredicted Reactivity

Boron donor ligands isoelectronic with classical organometallic systems are of interest in novel stoichiometric and catalytic reactions. The unusual ambiphilic character of the allenylidene ligand [LxM=C=C=CR2], which displays alternating electrophilic/nucleophilic reactivity at successive carbon centers, makes it interesting for a range of synthetically valuable organic transformations.

Simon Aldridge and co-workers, University of Oxford, UK, have reported the first iminoborylene complexes — isoelectric BN-containing analogues of allenylidene. The complexes, [CpFe(CO)(PCy3)(BNCAr2)]+, were synthesized by halide abstraction from 2 (see below). DFT calculations supported alternating α (boron),γ (carbon) electrophilicity similar to allenylidenes, however both boron complexes reacted with nucleophiles primarily at the sterically less hindered α (boron) center.
This unpredicted reactivity could lead to new routes to a range of organic compounds or their boron-containing analogues.

Scheme BN Containing Complexes with Unpredicted Reactivity

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