Olefin-Supported Rhenium(III) Terminal Oxo Complexes Generated by Nucleophilic Addition to a Cyclopentadienyl Ligand.

The reactivity of the oxo ReV β-diketiminate, OReCl2 (BDI), with various cyclopentadienide (Cp) sources has been investigated. As a result, we have developed a route to a new class of terminal oxo complexes of ReIII supported by olefin moieties of substituted cyclopentadienes. The success of this pathway is due to the electrophilic nature of the Cp ligand in the cation, [ORe(η5 -Cp)(BDI)]+ (3+ ), which allows for nucleophilic attack by a variety of reagents under mild conditions. In contrast, t BuNC was found to attack at the oxo moiety to produce isocyanate by oxygen atom transfer.