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Synthesis, Raman, X-ray diffraction, and density functional studies of antimony(III) heterotetracycles displaying intramolecular transannular interactions O → Sb

Structural Chemistry volume 24, pages 1555–1564 (2013)Cite this article

Abstract

A set of compounds of general formula [{S(C6H3S)2O}SbHal] [Hal = Cl (1), Br (2), I (3)] has been synthesized and studied by Raman and NMR spectroscopy as well as quantum chemical DFT calculations. X-ray diffraction studies of compound 2 revealed that the oxygen atom participates as donor and the antimony atom plays the role of acceptor, adopting a Ψ-distorted trigonal bi-pyramidal geometry, where the eight-membered central ring displays a boat–boat conformation. Furthermore, a series of DFT calculations was performed on compounds 1–3 as well as calculations on the non-synthesized heterotetracyclic systems [{S(C6H3S)2O}SbF] (4a) and the cation [{S(C6H3S)2O}Sb]+ (5a). The theoretic study at DFT level indicates as the electronegativity increases at exocyclic substituent along the set of compounds, the interaction is stronger. Moreover, the topological analysis of electronic density showed the existence of critical points along the O → Sb direction which prompted us to suggest the existence of a dative bond.

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Acknowledgments

Financial support of this work by CONACYT (Project 83157) is gratefully acknowledged. EGP and RRN fully acknowledge CONACYT for their scholarship.

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Authors and Affiliations

  1. Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Unidad Universitaria km 4.5 Carretera Pachuca-Tulancingo, 42184, Pachuca, HGO, Mexico

    Edmundo Guzmán-Percástegui, Julián Cruz-Borbolla, José G. Alvarado-Rodríguez, Noemí Andrade-López & Raúl Rojas-Navarrete

  2. Facultad de Química, Universidad Nacional Autónoma de México (UNAM), Ciudad Universitaria, Coyoacán, 04510, Mexico, Mexico

    Thangarasu Pandiyan

Authors
  1. Edmundo Guzmán-Percástegui
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  2. Julián Cruz-Borbolla
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  3. José G. Alvarado-Rodríguez
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  4. Noemí Andrade-López
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  5. Thangarasu Pandiyan
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  6. Raúl Rojas-Navarrete
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Correspondence to José G. Alvarado-Rodríguez.

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Guzmán-Percástegui, E., Cruz-Borbolla, J., Alvarado-Rodríguez, J.G. et al. Synthesis, Raman, X-ray diffraction, and density functional studies of antimony(III) heterotetracycles displaying intramolecular transannular interactions O → Sb. Struct Chem 24, 1555–1564 (2013). https://doi.org/10.1007/s11224-012-0173-1

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  • DOI: https://doi.org/10.1007/s11224-012-0173-1

Keywords

  • Hypervalence
  • Antimony–thiolate complexes
  • Secondary interactions
  • DFT calculations