Oxy-functionalization of olefins with neat and heterogenized binuclear V(IV)O and Fe(II)complexes: Effect of steric hindrance on product selectivity and output in homogeneous and heterogeneous phase

Article abstract of DOI:10.1016/j.mcat.2019.110424

Neat {[VO(sal₂bz)]₂; [Fe(sal₂bz)(H₂O)₂]₂·2H₂O} and zeolite-Y immobilized {[VO(sal₂bz)]₂-Y; [Fe(sal₂bz)(H₂O)₂]₂-Y} binuclear complexes have been prepared and characterized by spectroscopic techniques (IR, UV–vis), elemental analyses (CHN, ICP-OES), thermal study (TGA), scanning electron micrograph (SEM), adsorption study (BET)and X-ray diffraction (XRD)patterns. Neat (homogeneous)and immobilized (heterogeneous)complexes were employed as catalysts in the oxidation of olefins, namely, cyclohexene, limonene and α-pinene in the presence of 30% hydrogen peroxide. 100% conversion of cyclohexene and α-pinene was obtained while limonene was oxidized up to 90%. Homogeneous catalysts showed highly selective result as neat [VO(sal₂bz)]₂ complex has provided 87% cyclohexane-1,2-diol and neat [Fe(sal₂bz)(H₂O)₂]₂·2H₂O complex has provided 79% verbenone in oxidation of cyclohexene and α-pinene, respectively. We have observed that due to steric hindrance, formation of olefinic oxidation products increases on moving from α-pinene to limonene and limonene to cyclohexene. Additionally. recovered heterogeneous catalysts showed intact results up to two consecutive runs. Probable catalytic mechanism has been proposed for oxidation of cyclohexene.