Exploring the effect of hydroxylic and non-hydroxylic solvents on the reaction of [VIVO(β-diketonate)2] with 2-aminobenzoylhydrazide in aerobic and anaerobic conditions

Abstract

Refluxing [V^IVO(β-diketonate)₂], namely [V^IVO(acetylacetonate)₂] and [V^IVO(benzoylacetonate)₂], separately with an equivalent or excess amount of 2-aminobenzoylhydrazide (ah) in laboratory grade (LG) CH₃OH in aerobic conditions afforded non-oxidovanadium(IV) and oxidovanadium(V) complexes of the type [V^IV(L¹)₂] (1), [V^VO(L¹)(OCH₃)]₂ (3) and [V^IV(L²)₂] (2), and [V^VO(L²)(OCH₃)] (4), respectively. (L¹)²⁻ and (L²)²⁻ represent the dianionic forms of 2-aminobenzoylhydrazone of acetylacetone (H₂L¹) and benzoylacetone (H₂L²), respectively, (general abbreviation, H₂L), which was formed by the in situ condensation of ah with the respective coordinated [β-diketonate] in medium-to-good yield. The yield of different resulting products was dependent upon the ratio of ah to [V^IVO(β-diketonate)₂]. For example, the yield of 1 and 2 complexes increased significantly associated with a decrease in the amount of 3 and 4 with an increase in the molar ratio of ah. Upon replacing CH₃OH by a non-hydroxylic solvent, LG CHCl₃, the above reaction yielded only oxidovanadium(V) complexes of the type [V^VO(L¹)(OH)]₂ (5), [V^VO(L²)(OH)] (6) and [V^V₂O₃(L)₂] (7, 8) whereas, upon replacing CHCl₃ by another non-hydroxylic solvent, namely LG CH₃CN, only the respective [V^V₂O₃(L)₂] (7, 8) complex was isolated in 72–78% yield. However, upon performing the above reactions in the absence of air using dry CH₃OH or dry CHCl₃, only the respective [V^IV(L)₂] complex was obtained, suggesting that aerial oxygen was the oxidising agent and the type of pentavalent product formed was dependent upon the nature of solvent used. Complexes 3 and 4 were converted, respectively, to 7 and 8 on refluxing in LG CHCl₃via the respective unstable complex 5 and 6. The DFT calculated change in internal energy (ΔE) for the reactions 2[V^VO(L²)(OCH₃)] + 2H₂O → 2[V^VO(L²)(OH)] + 2CH₃OH and 2[V^VO(L²)(OH)] → [V^V₂O₃(L²)₂] + H₂O was, respectively, +3.61 and −7.42 kcal mol⁻¹, suggesting that the [V^VO(L²)(OH)] species was unstable and readily transformed to the stable [V^V₂O₃(L²)₂] complex. Upon one-electron reduction at an appropriate potential, each of 7 and 8 generated mixed-valence [(L)V^VO–(μ-O)–OV^IV(L)]⁻ species, which showed valence-delocalisation at room temperature and localisation at 77 K. Some of the complexes showed a wide range of toxicity in a dose-dependent manner against lung cancer cells comparable with that observed with cis-platin.