Phospholes with reduced pyramidal character from steric crowding. 2. Photoelectron spectral evidence for some electron delocalization in 1-(2,4-di-tert-butyl-6-methylphenyl)-3-methylphosphole

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Abstract

Photoelectron spectroscopy has been explored as a tool to measure the flattening of the phosphorus pyramid in a phosphole as caused by a large, sterically demanding P-substituent. Earlier PE spectra had shown no difference in ionization energies (IE) for simple phospholes and their tetrahydro derivatives (both around 8.0-8.45 eV). Calculations of the Koopmans IE at the Hartree-Fock 6-31G* level for 1-methylphospholane showed that, as is known for nitrogen, planarization at phosphorus markedly reduced the ionization energy value (8.74 to 6.29 eV). A reduction in IE also occurred on planarizing 1-methylphosphole, but to a lesser extent, being offset by increased electron delocalization (8.93 to 7.16 eV). This suggests that experimental comparison of IE for the unsaturated and saturated systems could be used to detect the presence of electron delocalization in the former. The IE experimentally determined for the crowded 1-(2,4-di-tert-butyl-6-methylphenyl)-3-methylphosphole was 7.9 eV, the lowest ever recorded for a phosphole. The corresponding phospholane had IE 7.55 eV. The difference in the values is attributed to electron delocalization in the phosphole. Calculations performed on the related model 1-(2-tert-butyl-4,6-dimethylphenyl)-phosphole showed that the P-substituent adopted an angle of 55.7° (DFT/6-31G* level; 57.6° at the HF/6-31* level) with respect to the C2-P-C5 plane (for P-phenyl, 67.1° and 68.3°, respectively).

Original languageEnglish
Pages (from-to)7808-7812
Number of pages5
JournalJournal of Organic Chemistry
Volume61
Issue number22
DOIs
Publication statusPublished - Nov 1 1996

ASJC Scopus subject areas

  • Organic Chemistry

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