The electron transmission spectra of 1,3,5-tri-tert-butyl-benzene, 2,4,6-tri-tert-butyl-pyridine, 2,4,6-tri-tert-butyl-phosphabenzene and 2,4,6-tri-tert-butyl,1,3,5-triphosphabenzene have been investigated and interpreted by means of quantum chemical calculations. Scaled virtual orbital energies obtained from calculations without employing diffuse functions provide good numerical values for the vertical electron attachment energies (VAEs). B3LYP/6-311+G* VAEs, calculated as the energy difference between the anion and the neutral molecule, were in good agreement with experiment, the molecules investigated here having VAEs of less than about 1 eV. The first anion state of phosphabenzene is predicted to lie at the edge of stability. The gradual replacement of CH units by phosphorus in p-systems results in a significant stabilization of the anionic states, which contrasts with the relative invariance of the electron donor properties. This behaviour can be explained by considering that for the P=C π-system both the interaction between the atomic levels (β) and the overlap is smaller than for the C=C π-system.
A. Modelli, B. Hajgató, J.F. Nixon, L. Nyulászi (2004). Anionic states of six-membered aromatic phosphorus heterocycles as studied by electron transmission spectroscopy and ab initio methods. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 108, 7440-7447 [10.1021/jp0480596].
Anionic states of six-membered aromatic phosphorus heterocycles as studied by electron transmission spectroscopy and ab initio methods.
MODELLI, ALBERTO;
2004
Abstract
The electron transmission spectra of 1,3,5-tri-tert-butyl-benzene, 2,4,6-tri-tert-butyl-pyridine, 2,4,6-tri-tert-butyl-phosphabenzene and 2,4,6-tri-tert-butyl,1,3,5-triphosphabenzene have been investigated and interpreted by means of quantum chemical calculations. Scaled virtual orbital energies obtained from calculations without employing diffuse functions provide good numerical values for the vertical electron attachment energies (VAEs). B3LYP/6-311+G* VAEs, calculated as the energy difference between the anion and the neutral molecule, were in good agreement with experiment, the molecules investigated here having VAEs of less than about 1 eV. The first anion state of phosphabenzene is predicted to lie at the edge of stability. The gradual replacement of CH units by phosphorus in p-systems results in a significant stabilization of the anionic states, which contrasts with the relative invariance of the electron donor properties. This behaviour can be explained by considering that for the P=C π-system both the interaction between the atomic levels (β) and the overlap is smaller than for the C=C π-system.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
