Organotransition metal complexes capable of forming metalloradicals have been an intriguing subject of study for the past fifty years. Of these, rhodium porphyrin complexes have proven particularly interesting due to their straightforward synthesis and unique reactivity; indeed, these complexes are responsible for some highly influential transformations of organic compounds, including rare C-H and C-C bond activations. The complexity and selectivity of rhodium porphyrins has been attractive for catalytic transformations, with specific interest in their usage for selective carbon monoxide reduction for fuel cell applications. This review will highlight historical and modern syntheses of rhodium porphyrins, as well as their respective reactions with small molecules and applications therein. The discussion will be limited to rhodium porphyrins consisting of four pyrrolic rings bridged with four methine units.
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