Peculiarities of fluoride activation of porphyrin and phthalocyanine catalysts by the example of zirconium and hafnium in the production of cyclic carbonates

•The fluoride additives increase the catalytical activity of Hf and Zr complexes by several orders of magnitude.•500 ppm of fluoride-activated HfCl4 catalyst is sufficient for efficient synthesis of carbonates.•(TON up to 2000).•Demetallation of the hafnium porphyrin complex during the cyclic carbonate synthesis was observed, while the phthalocyanine complex is stable. In this work, we have shown that fluoride additives can increase the catalytic activity of even 5- and 6-period metal complexes. Using tetraphenylporphyrin and phthalocyanine hafnium complexes as an example we were able to lower catalyst loading to 500 ppm. It was found out that after reaction tetraphenylporphyrin complex decomposed with the formation of meso‑tetraphenylporphyrin. Such process did not occur with the phthalocyanine complex. Moreover, in the presence of the fluoride additive hafnium tetrachloride showed high catalytic activity similar to both tetraphenylporphyrin and phthalocyanine comlpexes. [Display omitted]