Pyrrolylmethylene Appended Corrorin: Peripheral Coordination and Transformation to Pyridyl Incorporated Hemiporphycene Analogue

A pyrrolylmethylene appended corrorin 1 was synthesized and coordinated with [Rh(CO)2Cl]2 to afford 1-Rh with unique RhI-eta 2-CC bonding in addition to the coordination of the dipyrrin-like unit and a carbonyl ligand. Further oxidation of 1 afforded 2, exhibiting a hydrocorrorinone core, and it can be further transformed into pyrrolo[3,2c]pyridine incorporated hemiporphycene analogue 3 upon treatment with HOAc. The side chain modifies the reactivity of corrorin and effectively tunes the NIR absorption of the resulting porphyrinoids.

Automated summary

A pyrrolylmethylene appended corrorin 1 was synthesized and coordinated with [Rh(CO)2Cl]2 to form 1-Rh with unique RhI-eta 2-CC bonding. Further oxidation of 1 yielded 2, which exhibited a hydrocorrorinone core and could be transformed into pyrrolo[3,2c]pyridine derivative 3. The reactivity of corrorin and the near-infrared (NIR) absorption of the resulting porphyrinoids were effectively modified by the side chain.