Your browser doesn't support javascript.
loading
Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.
Saethre, L J; Berrah, N; Bozek, J D; Børve, K J; Carroll, T X; Kukk, E; Gard, G L; Winter, R; Thomas, T D.
Afiliação
  • Saethre LJ; Department of Chemistry, University of Bergen, N-5007 Bergen, Norway.
J Am Chem Soc ; 123(43): 10729-37, 2001 Oct 31.
Article em En | MEDLINE | ID: mdl-11674006
ABSTRACT
High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.
Buscar no Google
Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2001 Tipo de documento: Article País de afiliação: Noruega
Buscar no Google
Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2001 Tipo de documento: Article País de afiliação: Noruega