Dirhodium tetracarboxylate catalysts have long been known to catalyze the decomposition of diazo compounds to form putative dirhodium carbene intermediates that readily react with C-H bonds and olefins to afford C-C bonds and cyclopropanes, respectively. Screening several dirhodium complexes in a reaction with methyl-p-methoxyphenyl diazoacetate at -80�C showed that Rh2(TPA)4 (TPA = triphenylacetate) yields a long-lived intermediate species observable by UV-Visible spectroscopy. This intermediate was further characterized by Resonance Raman spectroscopy and low temperature 13C NMR via 13C isotopic labeling of the diazo starting material. Comparisons of the experimental data to computational models will be presented.

Identification and characterization of intermediate species in low temperature reactions between dirhodium carboxylates and organic diazo compounds

243rd National Meeting (2012)

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