Syntheses of Acyl Rhodium Porphyrins by Aldehydic Carbon−Hydrogen Bond Activation with Rh(III) Porphyrin Chloride and Methyl

Rhodium(III) porphyrin chloride reacted with aryl aldehydes in solvent-free conditions to give acyl
rhodium porphyrins. Selective aldehydic without any aromatic carbon−hydrogen bond activation (CHA)
was observed. At lower temperature, reduction and side products were found. Alkanals reacted poorly.
On the other hand, Rh(III) porphyrin methyl reacted more cleanly with both aryl and alkyl aldehydes.
These reactions provided a facile, convenient synthesis of acyl rhodium porphyrins. These activations
are unique CHA by high-valent Rh(III) species. Preliminary mechanistic experiments suggested that the
rhodium(III) porphyrin chloride initially formed a cationic rhodium(III) porphyrin via chloride dissociation
and then underwent oxidative addition or heterolysis to yield the product. On the other hand, rhodium(III)
porphyrin methyl underwent either oxidative addition or σ bond metathesis.