SEARCH

SEARCH BY CITATION

Chemistry Terms

Choose one or more boxes to highlight terms.

Keywords:

  • heavier group-14 analogous of formamide;
  • H-bond;
  • internal rotation barrier;
  • NBO analysis;
  • NEDA analysis

A theoretical study on heavier group-14 substituting effect on the essential property of formamide, strong hydrogen bond with water and internal rotational barrier was performed within the framework of natural bond orbital (NBO) analysis and based on the density functional theory calculation. For heavier group-14 analogues of formamide (YHONH2, Y = Si, Ge and Sn), the nN–πY=O conjugation strength does not always reduce as Y becomes heavier, for example, silaformamide and germaformamide have similar strength of delocalization. Heavier formamides prefer being H-bond donors to form FYO–H2O complexes to being H-bond acceptors to form FYH–H2O complexes. The NEDA analysis indicates that H-bond energies of FYO–H2O complexes increase as moving down group 14 due to concurrently stronger charge transfer (CT) and electrostatic attraction and for the FYH–H2O complexes H-bond strengths are similar. The model of CTs from FYO to H2O differs from that at FYH–H2O complexes, which are contributed not only by aligning lone-pair orbital of O but also by another lone-pair orbital. At two lowest lying excited states (the triplet and S1 excited states), formamide and its heavier analogues form double H-bonds with H2O molecule at the same time. The barrier heights of internal rotation become gradually low from C to Sn, formamide (15.73 kcal/mol) > silaformamide (11.73 kcal/mol) > germaformamide (9.45 kcal/mol) > stannaformamide (7.50 kcal/mol) at the CCSD(T)/aug-cc-pVTZ//B3LYP/cc-pVTZ level. NBO analysis indicates that the barrier does not only come from the nN[RIGHTWARDS ARROW]π*YO conjugation, and for heavier analogues of formamide, the nN[RIGHTWARDS ARROW]σ*YO hyperconjugation effect and steric effect considerably contribute to the overall rotational barrier. Copyright © 2013 John Wiley & Sons, Ltd.

Featured Compounds

VIEW

  1. 1 - 3
Compound 2
Molecular Weight:61.1154
Molecular Formula:H3NOSi
InChIKey:BQEQOCYKSQLUJZ-UHFFFAOYSA-N
View compound in article | Full details | Search for this compound
Compound 3
Molecular Weight:105.67
Molecular Formula:GeH3NO
InChIKey:MNGWBFOHSZDSGZ-UHFFFAOYSA-N
View compound in article | Full details | Search for this compound
Compound 4
Molecular Weight:151.74
Molecular Formula:H3NOSn
InChIKey:OJLGZUPRDSOHCG-UHFFFAOYSA-N
View compound in article | Full details | Search for this compound

VIEW

  1. 1 - 3