New Boron Complexes with Unpredicted Reactivity

New Boron Complexes with Unpredicted Reactivity

Author: ChemViews

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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