Competition between intramolecular hydrogen and pnictogen bonds in protonated systems

Goar Sánchez-Sanz, Cristina Trujillo, Ibon Alkorta, José Elguero

Research output: Contribution to journalArticlepeer-review

Abstract

A theoretical study of the competition between hydrogen (HB) and pnictogen bonds (ZB) in three different families of compounds, (Z)-1,2-disubstituted ethenes (Eth), 1,2-disubstituted benzenes (Phe) and 1,8-disubstituted naphthalenes (Naph), with a charged group, ZH3 + and a neutral one, Z′H2 (Z, Z′ = N, P, As) as interacting moieties, has been carried out. In those structures with a NH3 + motif, intramolecular hydrogen bond structures are minima while pnictogen interactions are transition states. The opposite is true for PH3 + and AsH3 + moieties. An analysis of isodesmic energies (Eiso), interaction energies (Eb) and deformation energies (Edef) shows that in Eth derivatives, the most stable compound corresponds to P+–N ZB while in the Phe and Naph ones, the N+–N HB interaction presents the largest negative isodesmic energy. Also, Eth and Phe derivatives show negative Eiso values for all the compounds under study; however, in some cases of Naph derivatives positive isodesmic energies have been found. The Atoms in Molecules (AIM) analysis of the electron density, natural bond orbital (NBO) second-order orbital energies and electron density shift maps (EDS) have been used to better understand these intramolecular interactions.

Original languageEnglish
Article number140
JournalTheoretical Chemistry Accounts
Volume135
Issue number5
DOIs
Publication statusPublished - 1 May 2016

Keywords

  • Hydrogen bonds
  • Interaction energy
  • Intramolecular interactions
  • MP2
  • Non-covalent interactions
  • Pnictogen bonds

Fingerprint

Dive into the research topics of 'Competition between intramolecular hydrogen and pnictogen bonds in protonated systems'. Together they form a unique fingerprint.

Cite this