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The obtained experimental results allow us to conclude that the dissociation-association mechanism nearly exclusively governs the phototransformation in thione heterocycles with high barriers for tautomerization (such as thione compounds with a five-membered ring), whereas the strictly intramolecular hydrogen-atom shift contributes to the mechanism of hydrogen-atom transfer in thione heterocycles with lower barriers (such as thione compounds with a six-membered ring).The mechanism of the Ru(II)-catalyzed anti-Markovnikov formal hydroalk
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