Concerted processes in supercritical fluids
The possibility of obtaining concerted mechanisms of chemical activation in supercritical fluids (SCFs) with the formation of a multicenter general transition state that includes a group of reagent atoms in which the subsequent breaking of chemical bonds and the formation of new chemical bonds start and proceed simultaneously is discussed. Two processes are considered that can occur only in SCF media: the reduction of anthracene in an isopropyl alcohol SCF and the impregnation of the photochromic compound spiroanthrooxazine (SAO) in a polycarbonate matrix in SC CO2 accompanied by an irreversible conformational rearrangement of the SAO structure. Concepts of the possible dependence of the concerted mechanism of the considered processes on the intertwining or entanglement of electron subsystems in forming multicenter transition states are developed. The decisive role of the electromagnetic component of a physical vacuum in obtaining a high degree of correlation in systems of entangled electrons is discussed.
Russian Journal Of Physical Chemistry A
International Academic Publishing Co
Russian Foundation for Basic Research [11-03-93962-YuAR_a, 11-03-12074-ofi-m-2011]; [1795.2012.3]