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X-Ray determination of the effective charges on sulfur and phosphorus atoms in chemical compounds

✍ Scribed by G. N. Dolenko; A. L. Litvin; V. P. Elin

Publisher: John Wiley and Sons
Year: 1992
Tongue: English
Weight: 681 KB
Volume: 3
Category: Article
ISSN: 1042-7163
DOI: 10.1002/hc.520030402

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✦ Synopsis

The dependencies of Ka line shifts of the P and S atoms on effective charges of the atoms, calculated by CNDO/S, CNDOIZ, INDO, and MNDO methods in the minimal and extended basis sets, have been investigated for model compounds. Good linear relationships between Ka shifts and atomic charges have been obtained for all cases investigated except for CNDO/2 and INDO calculations in the extended basis set. It is found that the P=S bond ionicity is a nearly constant value, whereas the P-S bond ionicity increases linearly with an increase in the positive charge of the central P atom. It is shown that the P and S atom charge in sulfides and phosphines containing no suhstituents with a strong M-effect at the central atom depend only on inductive substituent effects. Also, the positive charge on the central atom increases with the growth of the n-donor properties of substituents in sulfides and phosphines containing substituents exerting a strong M-effect, as well as in phosphoryl and thiophosphovyl compounds and sul fones.

non-empirical calculations with the ion charges. However, all the obtained relationships between the K a shifts and the atomic charges had two drawbacks: 1) they were untrue for the K a line iO Q8t 0.4 I 0 sl s " 0 A s stated in references 1-8, the K a line shifts of CND0/2 calculations in [lo]. Points represent calculations the 2nd Row element such as Al, Si, P, S and C1 carried out in the minimal basis set and circles represent are determined by the effective charges of these atcalculations carried out in the extended basis set. 1 H,S, 2 oms. This follows from comparison of the Kcu line thio hene, 3 CS, , 4 OCS, 5 S,, 6 SO,, 7 F,SO, 8 SO:-, 9 energies of free atoms and their ions obtained by SO!-, 10 SF,.

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