The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc.
Cobalt(III) Oxidation Pretreatment of Organic Phosphorus Compounds for a Spectrophotometric Determination of Phosphorus in Water.
