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Tetradentate square-planar acetylumbelliferone–nickel (II) complex formation: a DFT and TD-DFT study

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Abstract

During the study of electrodeposition of nickel, natural coumarins were used as brighteners and caused an improvement in the surface of deposited plates. We thought about the mechanism by which the coumarins adhere to nickel and the most probable chemical mechanism would be an organometallic complex formation between these coumarins and the transition metal. In this study, the formation of a highly stable complex between a coumarin derivative, acetylumbelliferone and nickel, is investigated theoretically in aqueous solution, using the Gaussian 09 and DFT method. The energies of the HOMO and LUMO boundary orbitals, the atomic charges and the molecular electrostatic potentials of the acetylumbelliferone–nickel (Ni-AC4) complex were determined, analyzed and allowed us to locate the nucleophilic and electrophilic sites of attack for the free donor and the complex. Time-dependent density functional theory (TD-DFT) with PCM was used to calculate the electronic transitions of formed complex using the ground state geometry from optimized complexes. Charge transfer between metal and ligand is the most important factor for the stabilization of the complex (Ni-(AC) 4); NBO analysis confirmed this finding and indicated that the 3d orbital energy level order is dx2-y2 > dz2 > dxz, dyz > dxy.

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Authors and Affiliations

  1. Laboratoire de Chimie Appliquée, Université 8 Mai 1945, BP 401, 24000, Guelma, Algeria

    Karima Belguidoum, Yamina Boulmokh, Fatima Zahra Hamamdia & Habiba Amira-Guebailia

  2. Laboratoire de Chimie Computationnelle Et Nanostructure, Université 8 Mai 1945, BP 401, 24000, Guelma, Algeria

    Fatiha Madi & Leila Nouar

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  1. Karima Belguidoum
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  2. Yamina Boulmokh
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Belguidoum, K., Boulmokh, Y., Hamamdia, F.Z. et al. Tetradentate square-planar acetylumbelliferone–nickel (II) complex formation: a DFT and TD-DFT study. Theor Chem Acc 141, 48 (2022). https://doi.org/10.1007/s00214-022-02903-8

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