Structural Chemistry

, Volume 27, Issue 3, pp 753–762 | Cite as

A computational study on [(PH2X)2]·+ homodimers involving intermolecular two-center three-electron bonds

Original Research

Abstract

A computational study at CCSD(T) theoretical level has been carried out on radical cation [(PH2X)2]·+ homodimers. Four stable minima configurations have been found for seven substituted phosphine derivatives, X = H, CH3, CCH, NC, OH, F and Cl. The most stable minimum presents an intermolecular two-center three-electron P···P bond except for X = CCH. The other three minima correspond to an alternative P···P pnicogen bonded complex, to a P···X contact and the last one to the complex resulting from a proton transfer, PH3X+:PHX·. The complexes obtained have been compared with those of the corresponding neutral ones, (PH2X)2, and the analogous protonated ones, PH3X+:PH2X, recently described in the literature. The spin and charge densities of the complexes have been examined. The electronic characteristics of the complexes have been analyzed with the NBO and AIM methods. The results obtained for the spin density, charge and NBO are coherent for all the complexes.

Keywords

Pnicogen bonds Radical cation phosphines Two-center three-electron Molecular electrostatic potentials Stabilizing charge transfer energies 

Notes

Acknowledgments

This work has been supported by the Spanish Ministerio de Economía y Competitividad (CTQ2012-35513-C02-02) and Comunidad Autónoma de Madrid (S2013/MIT-2841, Fotocarbon). Computer, storage and other resources from the CTI (CSIC) are gratefully acknowledged. One of us (M.M.-L.) thanks the Ministerio de Economía y Competitividad for her contract.

Supplementary material

11224_2015_617_MOESM1_ESM.doc (2.1 mb)
Molecular graphs, CCSD(T)/CBS energy and geometry of the minima of the system calculated. Bond lengths and angles values of both monomers, A and B, in the complexes. Net charge values of monomers A in the complexes.(DOC 2130 kb)

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Marta Marín-Luna
    • 1
  • Ibon Alkorta
    • 1
  • José Elguero
    • 1
  1. 1.Instituto de Química Médica (CSIC)MadridSpain

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