Sharpless et al. have described, while performing the molybdenum-catalyzed epoxidation reaction of olefins using alkyl hydroperoxides, that the molybdenum-oxo moiety is an active catalytic species. Thus, continuous efforts have been made to synthesize molybdenum-oxo complexes of different ligand environments. While plenty of such works on molybdenum porphyrins are reported in the literature, related molybdenum corroles are very less reported. The synthesis and characterization of two new oxo-molybdenum­(V)-corrolato complexes are described herein. Both the complexes have been fully characterized by several spectroscopic techniques in conjunction with single-crystal X-ray diffraction analysis. The efficacy of the oxo-molybdenum­(V)-corrolato complexes for the catalytic epoxidation reaction of olefins with the help of hydroperoxides has also been explored. The catalytic application of oxo-molybdenum­(V)-corrolato complexes in the epoxidation reaction has not been reported earlier. A mechanism has been proposed to explain the experimental findings.

A new method of activating corrole macrocycles via an in situ generated SCN radical has been developed at very mild conditions at room temperature. This photoredox reaction resulted in the generation of tetrathiocyanatocorroles in good yields. The synthesis of tetrathiocyanatocorroles was never reported earlier. Single-crystal XRD analysis reveals that the insertion of four thiocyanate moieties at the four β-pyrrolic positions has imparted significant distortion to the corrole macrocycle. The generated tetrathiocyanatocorroles are different from the parent corroles in many ways. The photophysical properties of the newly synthesized tetrathiocyanatocorroles are dramatically altered from the parent corroles. The absorption feature of these modified corrole derivatives (both position and intensity) bears a nice similarity with the chlorophyll-a macrocycle. Thus, these newly synthesized molecules can be considered as spectroscopic model systems for chlorophyll-a pigments. The observed absorption and emission spectra of these tetrathiocyanatocorroles certainly point out that these newly developed ligand scaffolds and their various metal complexes will have immense potential as pigments in solar cells and also as NIR-emissive dyes. The observed C-H•••Au weak interactions in a representative Au(III)-corrole complex point out that these complexes are capable of activating the unfunctionalized C−H groups and thus will have potential implications in C-H activation reactions.

The newly synthesized bis(thiocyanato)-triphenylcorrole has turned out to be a good corrole based precursor for the facile synthesis of thiol protected gold nanoparticles (Au NPs).