Theoretical study of the stability and NMR spectroscopic properties of vanadium(V) complexes
- 5 Downloads
Several vanadium(V) complexes have been investigated as possible antidiabetic and anticancer therapeutic agents. Among these, vanadium(V) complexes linked to tridentate ONO Schiff bases stand out for their potential in the treatment for cancer. However, further studies are necessary in order to learn about their specific action at the cellular level. We investigate structural and spectroscopic properties of these particular complexes, which are formed by a Schiff base linked to a [VO2]+ ion that contains different functional groups. Molecular structure optimizations of these vanadium-containing complexes were performed by the ONIOM (QM1:QM2) method, where the high layer (complexes) were described by density functional theory methods whereas the low layer (eight water molecules) were described by the HF approach. Various solvation models were utilized; however, the introduction of both implicit (using a solvation model based on density, SMD) and explicit (eight water molecules) solvation improves the stability of the systems. Interestingly, we found that the location of the explicit water molecules in the different octahydrated vanadium complexes was conserved surrounding the oxo-vanadate moiety. A detailed analysis of the chemical shift (δ) values for 1H, 13C and 51V is presented based on the ONIOM optimized geometries using the gauge-independent atomic orbital methodology. For obtaining accurately chemical shifts, the complete basis set using the correlation-consistent Dunning basis sets from double-ξ to quadruple-ξ and the Ahlrichs basis set were utilized. The results from the methodology presented here are consistent with those reported experimentally for 1H. Again, the inclusion of explicit water molecules in the inner solvation shell during the calculation of the chemical shifts was crucial. The analysis of solvation energies also indicates the relevance of including explicit water molecules as the main stabilization factor suggesting the central role of intermolecular interaction in the stability of the metallic complexes. From this analysis, a possible vanadium complex candidate for further evaluation in the cellular environment is suggested. This work not only provides evidence of a suitable methodology for studying the structural and spectroscopic properties of vanadium complexes but also highlights the relevance of explicitly including water molecules in their inner shell.
KeywordsVanadium(V) complexes Schiff bases NMR spectroscopy ONIOM method CBS limit Solvent effect
L. Noriega thanks CONACYT (Mexico) for financial support (Ph.D. fellowship CVU: 697889). The authors thankfully acknowledge the computer resources, technical expertise and support provided by the Laboratorio Nacional de Supercómputo del Sureste de México, the CONACYT network of national laboratories, the computer resources of the Laboratorio de Supercómputo y Visualización en Paralelo at the Universidad Autónoma Metropolitana-Iztapalapa, and the Project 100256733-VIEP 2019 (VIEP-BUAP, Mexico) as well as the PRODEP Academic Group BUAP-CA-263 (SEP, Mexico).
- 2.Urquiola C, Vieites M, Aguirre G, Marín A, Solano B, Arrambide G, Nobñía P, Lavaggi ML, Torre MH, González M, Monge A, Gambino D, Cerecetto H (2006) Improving anti-trypanosomal activity of 3-aminoquinoxaline-2-carbonitrile N1,N4-dioxide derivatives by complexation with vanadium. Bioor Med Chem 14–16:5503–5509CrossRefGoogle Scholar
- 12.Ebrahimipour SY, Sheikhshoaie I, Kautz AC, Ameri M, Pasban-Aliabadi H, Rudbari HA, Bruno G, Janiak C (2015) Mono-and dioxido-vanadium(V) complexes of tridentate ONO Schiff base ligand: synthesis, spectral characterization, X-ray structure, and anticancer activity. Polyhedron 93:99–105CrossRefGoogle Scholar
- 15.Dapprich S, Komáromi I, Byun KS, Morokuma K, Frisch MJ (1999) A new ONIOM implementation in Gaussian 98. 1. The calculation of energies, gradients and vibrational frequencies and electric field derivatives. J Mol Struct (Theochem) 462:1–21. https://doi.org/10.1016/s0166-1280(98)00475-8 CrossRefGoogle Scholar
- 27.Melendez FJ, Castro ME, Perez-Aguilar JM, Caballero NA, Noriega L, González-Vergara E (2018) Computational study of aqueous solvation of vanadium(V) complexes. In: Conference proceedings of international supercomputing conference in México (ISUM 2018), vol CCIS 948. Springer, BerlinGoogle Scholar
- 29.Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 120:215–241CrossRefGoogle Scholar
- 36.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE Jr, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian, Inc., Wallingford, CTGoogle Scholar
- 37.X-ray crystallographic data from http://www.ccdc.cam.ac.uk/ (last accessed Jan 17, 2017) or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK
- 42.Kwiatkowski E, Romanowski G, Nowicki W, Kwiatkowski M, Suwinska K (2003) Dioxovanadium(V) Schiff base complexes of N-methyl-1,2-diaminoethane and 2-methyl-1,2-diaminopropane with aromatic o-hydroxyaldehydes and o-hydroxyketones: synthesis, characterization, catalytic properties and structure. Polyhedron 22:1009–1018CrossRefGoogle Scholar