Relationship of the charge characteristics of sulfur and phosphorus atoms in organic sulfides and phosphines to the σ-constants of the substituents at these atoms
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Correlations were obtained between the shifts of the Kα-lines of sulfur and phosphorus (proportional to the charges on these atoms) and the sums of the inductive and resonance substituent constants in the series of organic sulfides and phosphines.
The investigated phosphines are divided into two types according to the dependence of ΔPKα on the sums of the σ-constants of the substituents: those that contain and those that do not contain P-O and P-N bonds.
For sulfides and phosphines that do not contain P-O and P-N bonds, the charge on the S and P atoms is determined chiefly by the inductive effects of the substituents. An explanation for the large contribution of the mesomeric effect to the value of the charge on the P atom and their direction for phosphines containing P-O or P-N bonds is proposed.
KeywordsSulfur Phosphorus Sulfide Phosphine Large Contribution
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