Ruthenium-Induced Decomposition of Hexamethylenetetramine as a Tool for the Acid-Free Sommelet Reaction in Aqueous Medium

Hexamethylenetetramine (HMTA) is one of the most versatile and most utilized nitrogen-containing heterocyclic compounds in academia and industry. Most of the reactions involving HMTA employ stoichiometric or excess amounts of acid, which hamper the sustainability of the reactions. Herein, we report the first example of the ruthenium-mediated decomposition of HMTA at room temperature, supported by a detailed mechanistic study using thermogravimetric analysis/differential thermal analysis, variable-temperature NMR, UV-vis spectroscopy, and density functional theory techniques. The mechanism study also involves a comparison of the decomposition of HMTA, protonated HMTA, [RuCl