PM3 semiempirical calculations of lithium-cation and proton affinities for XYZPO and XYSO2 compounds
✍ Scribed by Jean-François Gal; Ilmar Koppel; Riho Kurg; Pierre-Charles Maria
- Publisher
- John Wiley and Sons
- Year
- 1996
- Tongue
- English
- Weight
- 850 KB
- Volume
- 59
- Category
- Article
- ISSN
- 0020-7608
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✦ Synopsis
Proton affinities (PAS) of a series of phosphorous compounds bearing the phosphoryl function have been calculated using AM1 and PM3, as well as lithium-cation affinities (LCAs) using the recent PM3 lithium parametrization. Sulfonyl derivatives PAS and LCAs have been also calculated using PM3. The Li+ cation can be bonded in a "chelate" form with the two oxygens of the sulfonyl group. Nevertheless, the "linear" adduct, with the lithium-oxygen bond collinear with one of the S=O bonds, is more stable. This is confirmed by ab initio calculations on Me,SO,-Li+ adducts.
Sons, Inc. 0 1996 John Wiley & of articles by Buncel [ l l and Modro [ 2 ] and their co-workers are of special interest in this regard.
Inhibition or catalysis were evidenced, depending on the nature of the alkali-metal cation, nucleophile counterion, substrate, and medium. The effect of the alkali-metal ion was analyzed in terms of the differential interaction with the nucleophile and with the transition-state complex