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Energetic and electronic study of indole derivatives

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Abstract

A detailed energetic and structural analysis of indole derivatives is performed by combining the results of B3LYP calculations with the data provided from the application of the natural bond orbital (NBO) theory. The following electron-donating and electron-accepting substituents have been considered: NO, NO2, CN, CH3, F, OCH3, OH and NH2. By using a homodesmic reaction, the substituent effect stabilization energies are evaluated. It is shown that the electron-donating and electron-accepting groups originate opposite effects when they interact with the indole ring. Attention is also given to the relative stabilization of the different substitution sites and of the different orientations of the substituents. In order to shed light into the origin of the global energetic effects of the indole substitution, the deletion and second-order perturbation methods implemented in the NBO analysis are applied. Special emphasis is paid to the effect of the endo- and exocyclic π-delocalizations. Connecting certain substituents to specific carbon centers leads to the formation of intramolecular H-bonds, which are here characterized by using geometrical and electronic descriptors. Their impact on the molecular stability and their interplay with the π-electron delocalization is investigated.

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Authors and Affiliations

  1. Centre of Chemistry – Coimbra, Faculty of Pharmacy, University of Coimbra, 3000-548, Coimbra, Portugal

    A. J. Lopes Jesus

  2. Department of Chemistry, University of Coimbra, 3004-535, Coimbra, Portugal

    J. S. Redinha

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  1. A. J. Lopes Jesus
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  2. J. S. Redinha
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Correspondence to A. J. Lopes Jesus.

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Lopes Jesus, A.J., Redinha, J.S. Energetic and electronic study of indole derivatives. Struct Chem 27, 809–820 (2016). https://doi.org/10.1007/s11224-015-0635-3

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