Title: Theoretical and experimental reevaluation of the basicity of lambda(3)-phosphinine
Authors: Pham-Tran, NN ×
Bouchoux, G
Delaere, D
Nguyen, Minh Tho #
Issue Date: Mar-2005
Series Title: Journal of Physical Chemistry A vol:109 issue:12 pages:2957-2963
Conference: date:Univ Louvain, Dept Chem, B-3001 Heverlee, Belgium; Ecole Polytech, Dept Chim DCMR, Lab Mecanismes React, F-91128 Palaiseau, France
Abstract: We have investigated the basicity of phosphinine (C5H5P, phosphabenzene) in reevaluating its proton affinity (PA) and gas-phase basicity (GB) and the pK(a), value of its protonated form. As a necessary step, we have first determined its gas-phase proton affinity. Using both mass spectrometric and quantum chemical methods, we have obtained the values PA(C5H5P) = 195.8 +/- 1.0 kcal mol(-1) and GB(298)(C5H5P) = 188.1 +/- 1.0 kcal mol(-1), in good agreement with previous results. We then derived a value of pK(a)(C5H6P+) = -16.1 +/- 1.0 in aqueous solution using three different approaches: the latter markedly differs from the currently available value of -10. The reason for such a discrepancy in the pK(a) of protonated phosphinine in solution is discussed. In the theoretical determination of PAs, evaluation of the basis set superposition error (BSSE) showed that this effect is quite small, being 0.1-0.2 kcal mol(-1) for phosphinine, when a density functional theory (DFT) method in conjunction with a large basis set were used.
ISSN: 1089-5639
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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