Phenomenological Theory of Electron and Methyl Transfer Reactions in Organic Crystals

Theoretical Study on the Topochemical Nature in the Initiation Process of the Solid-State Thermal Isomerization Reaction of Methyl 4-(Dimethylamino)benzenesulfonate

“…Here, our recent work has shown that the conformation of the methylsulfo group in the crystal is realized only in the crystal but not in the free space. 6 Although many studies on this solid-state reaction have been carried out so far, [6][7][8][9][10][11][12][13][14] the mechanism of this reaction still remains unsolved. Gavezzotti and Simonetta proposed possible ionic intermediates, shown in Figure 1c, in view of the unique crystal structure above.…”

“…Although many studies on this solid-state reaction have been carried out so far, − the mechanism of this reaction still remains unsolved. Gavezzotti and Simonetta proposed possible ionic intermediates, shown in Figure c, in view of the unique crystal structure above .…”

“…Gavezzotti and Simonetta proposed possible ionic intermediates, shown in Figure c, in view of the unique crystal structure above . However, molecular structures, total energies, and electronic properties of such intermediates have not yet been characterized . On the other hand, the motional analysis for the MDBS crystal by Sarma and Dunitz, with reference to collective rotation of MDBS molecules around the respective molecular long axes in the crystal, has not clarified whether this reaction could be initiated by such a motion.…”