Several examples of unusual, high oxidation state Fischer carbenes have been synthesized by treating rhenium acyl and imino-acyl intermediates, generated by direct insertion, with electrophilic reagents. Experimental and computational studies suggest that, as expected, the carbene ligands are electrophilic at carbon. Analysis of the <sup>13</sup>C NMR shift of the carbene carbon and calculated NBO charge revealed a strong correlation between electrophilicity and <sup>13</sup>C NMR shift, which suggests the electrophilicity of the carbene is tunable, with the substituent attached to carbene carbon having the most influence. In addition to exhibiting substitution chemistry at the carbene carbon, these complexes were also found to be precatalysts for the hydrosilylation of unsaturated substrates.

Synthesis, reactivity, and catalytic activity of Re(III) and Re(V) Fischer carbenes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.