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The kinetics of the chlorine isotopic exchange between chloride ion at O,O‐diarylphosphorochloridates or O,O‐diarylphosphorochloridothionates
Author(s) -
ReimschüSsel W.,
Mikołajczyk M.,
Ślebockatilk H.,
Gajl M.
Publication year - 1980
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550121207
Subject(s) - chemistry , chlorine , kinetics , entropy of activation , intramolecular force , enthalpy , reaction rate constant , medicinal chemistry , acetonitrile , reactivity (psychology) , chloride , activated complex , inorganic chemistry , sulfur , stereochemistry , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
Abstract The kinetics of the chlorine isotopic exchange reaction between tetraethylammonium chloride‐ 36 Cl and O,O‐diarylphosphorochloridates ( p ‐RC 6 H 4 O) 2 POCl or O,O‐diarylphosphorochloridothionates ( p ‐RC 6 H 4 O) 2 PSCl has been studied in acetonitrile solution. Good Hammett's correlations of the rate constants with Taft's σ 0 constants were obtained. The values of the reaction constants ρ were found identical for phosphoryl and thiophosphoryl compounds. In comparison with oxygen in the phosphoryl group, the sulfur atom exhibits an electron‐donating effect (Δσ 0 ∼ 0.80). No correlation has been found for the enthalpy and entropy of activation. The effect of the substituents aryloxy groups, oxygen, or sulfur atoms in the phosphoryl group on the kinetics of the S N 2‐P reaction is discussed. The reactivity of the investigated compounds is determined by the extent of the positive charge localized on the phosphorus atom. The positive charge is formed by the direct interactions of the substituents with the reaction center and the indirect–intramolecular interactions revealed in the structure of the compound.