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Issue 33, 2017
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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

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Abstract

Refluxing [VIVO(β-diketonate)2], namely [VIVO(acetylacetonate)2] and [VIVO(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 [VIV(L1)2] (1), [VVO(L1)(OCH3)]2 (3) and [VIV(L2)2] (2), and [VVO(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 [VIVO(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 [VVO(L1)(OH)]2 (5), [VVO(L2)(OH)] (6) and [VV2O3(L)2] (7, 8) whereas, upon replacing CHCl3 by another non-hydroxylic solvent, namely LG CH3CN, only the respective [VV2O3(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 [VIV(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[VVO(L2)(OCH3)] + 2H2O → 2[VVO(L2)(OH)] + 2CH3OH and 2[VVO(L2)(OH)] → [VV2O3(L2)2] + H2O was, respectively, +3.61 and −7.42 kcal mol−1, suggesting that the [VVO(L2)(OH)] species was unstable and readily transformed to the stable [VV2O3(L2)2] complex. Upon one-electron reduction at an appropriate potential, each of 7 and 8 generated mixed-valence [(L)VVO–(μ-O)–OVIV(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.

Graphical abstract: 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

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Publication details

The article was received on 16 May 2017, accepted on 14 Jul 2017 and first published on 14 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT01776F
Citation: Dalton Trans., 2017,46, 10963-10985
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    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

    N. Biswas, D. Patra, B. Mondal, S. Bera, S. Acharyya, A. K. Biswas, T. K. Mukhopadhyay, A. Pal, M. G. B. Drew and T. Ghosh, Dalton Trans., 2017, 46, 10963
    DOI: 10.1039/C7DT01776F

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