{"id":9508,"date":"2011-05-24T17:09:17","date_gmt":"2011-05-24T15:09:17","guid":{"rendered":"https:\/\/web.computaex.es\/?page_id=9508"},"modified":"2025-08-27T09:20:05","modified_gmt":"2025-08-27T07:20:05","slug":"9508-2","status":"publish","type":"page","link":"https:\/\/computaex.es\/en\/publicaciones\/9508-2\/","title":{"rendered":"Mechanistic Insights on the Ruthenium-Catalyzed Hydrogenation of Amides \u2013 C\u2013N vs. C\u2013O Cleavage"},"content":{"rendered":"
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David Cantillo:\u00a0Mechanistic Insights on the Ruthenium-Catalyzed Hydrogenation of Amides \u2013 C\u2013N vs. C\u2013O Cleavage<\/strong>. European Journal of Inorganic Chemistry. Mayo de 2011, 3008-3013.<\/p>\n

Abstract<\/strong>
\nRuthenium-catalyzed amide hydrogenation was thoroughly explored by means of DFT calculations. All the plausible pathways, including those involving the amide or imine tautomer, were assessed. The classical C\u2013O cleavage and the recently reported C\u2013N cleavage were compared by employing a bipyridyl-based RuII<\/sup>\u00a0pincer complex as catalyst in the calculations. The study reveals that C\u2013O cleavage can be achieved directly over the amide substrate or its imine tautomer, since the computed pathways show analogous energy barriers. In addition, the mechanism for the novel C\u2013N cleavage was elucidated by modeling all the reasonable intermediates and transition structures. The computed energy barrier is lower than that for C\u2013O cleavage by more than 10 kcal\u2009mol\u20131<\/sup>, thus explaining the observed selectivity. The key role of the aromatization\/dearomatization processes during the transformation is also disclosed.<\/p>\n<\/div>\n<\/div>\n<\/div>\n

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