In the present work, the first data on the catalytic activity of d-metal complexes of petroleum porphyrins obtained via two-stage re-metallization (acid demetallization with subsequent metalation) of high-purity petroleum vanadyl porphyrins are presented. During acid demetallization of petroleum vanadyl porphyrins, the highest yield (49%) and spectral purity of free petroporphyrin bases were achieved with concentrated sulfuric acid and a diluted solution of vanadyl porphyrins in chloroform. In the series of divalent cations of Mn, Fe, Co, Ni, Cu, and Zn, only the last four metals are complexed with demetallated petroporphyrins without significant changes in their component composition, whereas the interaction with Mn and Fe cations causes an evident structural transformation or even full degradation of petroporphyrin macrocycles, respectively. The composition and spectral purity of petroleum porphyrin-containing reactants and products were analyzed by FT-IR, UV-Vis, NMR, and MALDI-TOF mass spectroscopic methods. The obtained petroporphyrin-based d-metal complexes were assayed by the reaction of 2-mercaptoethanol oxidative dimerization, in which the copper porphyrins exhibited the highest catalytic activity.

The composition of purified vanadyl porphyrins recovered from the resins of heavy oils possessing high and low vanadium contents was investigated. Vanadium content in the resins of the heavy oils under study differs by a factor of ca. 15. To recover and purify vanadyl porphyrins from the resins, extraction by N,N–dimethylformamide (DMF) with subsequent two-stage column chromatography on silica gel and sulfocationite were employed. The change of structural-group composition and content of vanadyl porphyrins in the products obtained at each stage was evaluated using Fourier IR and UV-Vis spectroscopy. Analysis of the purified vanadyl porphyrins using MALDI mass spectrometry determined distribution of their most abundant types (etio- and DPEP) and identified C₂₇–C₃₉ homologs for the resins possessing high vanadium content and C₂₈–C₃₉ homologs for the resins with low vanadium content.