Synthesis, structure, solution behavior, reactivity and biological evaluation of oxidovanadium(iv/v) thiosemicarbazone complexes

Saswati 1 , Adão P 2 , Majumder S 3 , Dash SP 4 , Roy S 5 , Kuznetsov ML 2 Show all authors , Costa Pessoa J 2 , Gomes CSB 2 , Hardikar MR 6 , Tiekink ERT 7 , Dinda R 1

Affiliations 

  • 1 Department of Chemistry, National Institute of Technology, Rourkela 769008, Odisha, India. [email protected]
  • 2 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. [email protected]
  • 3 Department of Chemistry, National Institute of Technology, Rourkela 769008, Odisha, India. [email protected] and Darmstadt University of Technology, Clemens-Schöpf Institute of Organic Chemistry and Biochemistry, Alarich-Weiss Str. 4, 64287 Darmstadt, Germany
  • 4 Department of Chemistry, National Institute of Technology, Rourkela 769008, Odisha, India. [email protected] and Department of Basic Sciences, Parala Maharaja Engineering College, Sitalapalli, Brahmapur, Odisha 761003, India
  • 5 Department of Chemistry, National Institute of Technology, Rourkela 769008, Odisha, India. [email protected] and Department of Chemistry, Indian Institute of Technology, Kanpur 208016, Uttar Pradesh, India
  • 6 Biometry and Nutrition Group, Agharkar Research Institute, G.G. Agrakar Road, Pune 411004, India
  • 7 Research Centre for Crystalline Materials, School of Science and Technology, Sunway University, Bandar Sunway, Selangor Darul Ehsan 47500, Malaysia
Dalton Trans, 2018 Aug 21;47(33):11358-11374.
PMID: 30059099 DOI: 10.1039/c8dt01668b

Abstract

The synthesis and characterization of an oxidovanadium(iv) [VIVO(L)(acac)] (1) and of two dioxidovanadium(v) [VVO2(L')] (2) and [VVO2(L)] (2a) complexes of the Schiff base formed from the reaction of 4-(p-fluorophenyl) thiosemicarbazone with pyridine-2-aldehyde (HL) are described. The oxidovanadium(iv) species [VIVO(L)(acac)] (1) was synthesized by the reaction of VIVO(acac)2 with the thiosemicarbazone HL in refluxing ethanol. The recrystallization of [VIVO(L)(acac)] (1) in DMF, CH3CN or EtOH gave the same product i.e. the dioxidovanadium(v) complex [VVO2(L)] (2a); however, upon recrystallization of 1 in DMSO a distinct compound [VVO2(L')] (2) was formed, wherein the original ligand L- is transformed to a rearranged one, L'-. In the presence of DMSO the ligand in complex 1 is found to undergo methylation at the carbon centre attached to imine nitrogen (aldimine) and transformed to the corresponding VVO2-species through in situ reaction. The synthesized HL and the metal complexes were characterized by elemental analysis, IR, UV-Vis, NMR and EPR spectroscopy. The molecular structure of [VVO2(L')] (2) was determined by single crystal X-ray crystallography. The methylation of various other ligands and complexes prepared from different vanadium precursors under similar reaction conditions was also attempted and it was confirmed that the imine methylation observed is both ligand and metal precursor specific. Complexes 1 and 2 show in vitro insulin-like activity against insulin responsive L6 myoblast cells, higher than VIVO(acac)2, with complex 1 being more potent. In addition, the in vitro cytotoxicity studies of HL, and of complexes 1 and 2 against the MCF-7 and Vero cell lines were also done. The ligand is not cytotoxic and complex 2 is significantly more cytotoxic than 1. DAPI staining experiments indicate that an increase in the time of incubation and an increase of concentration of the complexes lead to the increase in cell death.

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