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Structure and bonding in NbX5 X = (F, Cl, Br and I) complexes: a molecular orbital perspective in the C–H bond activation

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Abstract

In the present work, theoretical studies of the reactivity and stability of the NbX5 complexes (X = F, Cl, Br and I) were carried out in the methane C–H bond activation. To study the chemical bonds formation of these complexes, an energy decomposition analysis was performed together with QTAIM calculations. The main results indicated that the interaction and binding energies are higher for NbF5 in relation to the halogen series. The niobium complexes gaps are influenced by the electronegativity of the halogens and the Nb–X bonding lengths. According to the energy diagram, the electrons less connected to the bond are σNb–I; on the other hand, the best electron acceptor is σ*Nb–F. The QTAIM calculations confirmed stronger Nb–X chemical bonds in NbF5 complexes. Regarding the reactivity of the niobium complexes, the overall results indicate better thermodynamic and kinetic conditions for the NbF5 complex.

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Acknowledgements

The authors wish to thank the Brazilian financial agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior/Ministério da Defesa (CAPES/MD) for financial support, and the Federal University of Lavras (UFLA) for providing the physical infrastructure and working space. This work was also supported by Excellence project FIM.

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Authors and Affiliations

  1. Department of Chemistry, Federal University of Lavras, University Campus, Lavras, MG, 37200-000, Brazil

    Telles Cardoso Silva, Maíra dos Santos Pires, Alexandre Alves de Castro, Lívia Clara Tavares Lacerda & Teodorico Castro Ramalho

  2. Institute of Chemistry, Department of Physical Chemistry, Fluminense Federal University, Outeiro de São João Baptista, Niteroi, Rio de Janeiro, 24020-141, Brazil

    Marcus Vinícius Juliaci Rocha

  3. Center for Basic and Applied Research, Faculty of Informatics and Management, University of Hradec Kralove, Hradec Kralove, Czech Republic

    Teodorico Castro Ramalho

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  1. Telles Cardoso Silva
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Correspondence to Teodorico Castro Ramalho.

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Silva, T.C., Pires, M.d.S., de Castro, A.A. et al. Structure and bonding in NbX5 X = (F, Cl, Br and I) complexes: a molecular orbital perspective in the C–H bond activation. Theor Chem Acc 137, 146 (2018). https://doi.org/10.1007/s00214-018-2348-3

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