Toward a planar σ3-phosphorus

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Abstract

Correlated ab initio calculations show that the near 20 kcal/mol inversion barrier about phosphorus in phosphole can be reduced to 4.0 kcal/mol (CCSD(T)/6-311G(2D)//MP2/6-311G(2D)) by incorporating two σ23-phosphorus atoms into the five-membered ring, which decrease the ring strain. If the σ23-phosphorus atom is situated in α-position from the σ3-phosphorus atom, the planar structure is more stable with respect to the minimum energy structure than with a β-positioned σ23-phosphorus atom. The planar structures obtained show significant bond length equalization, characteristic for aromatic compounds. For systems having low inversion barrier, the bond length equalization is still significant for the nonplanar structures, which are minima on the potential energy surface. The nonbonding orbital of phosphorus in these cases is mixed considerably with the π-system. The bond lengths tend toward equalization. These facts indicate that aromatic stabilization has a considerable impact on these nonplanar molecules and is presumably influencing their chemical reactivity as well.

Original languageEnglish
Pages (from-to)6194-6198
Number of pages5
JournalJournal of Physical Chemistry
Volume100
Issue number15
Publication statusPublished - 1996

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Phosphorus
phosphorus
Bond length
Atoms
planar structures
atoms
inversions
Chemical reactivity
Potential energy surfaces
aromatic compounds
Aromatic compounds
rings
reactivity
Stabilization
stabilization
potential energy
orbitals
Molecules
molecules
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

Toward a planar σ3-phosphorus. / Nyulászi, L.

In: Journal of Physical Chemistry, Vol. 100, No. 15, 1996, p. 6194-6198.

Research output: Contribution to journalArticle

Nyulászi, L. / Toward a planar σ3-phosphorus. In: Journal of Physical Chemistry. 1996 ; Vol. 100, No. 15. pp. 6194-6198.
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