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Mechanism of the Manganese-Pincer Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols.

著者 Luque Urrutia JA , Solà M , Milstein D , Poater A
J Am Chem Soc.2019 Jan 11 ; ():.
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A recent study showed that a Mn-pincer could catalyze the acceptorless dehydrogenative coupling of nitriles and alco-hols to yield acrylonitriles. The reaction mechanism pro-posed in that work contained some intermediates that, in most of the cases, were not characterized. Moreover, one of the intermediates involved a charged separation, which is unlikely in apolar solvents. To clarify the reaction mecha-nism of this critical reaction, we decided to perform a DFT study. Our results prove the existence of a cooperative effect of the metal and the ligand in several steps of the catalytic cycle. We also find the presence of several equilib-ria between isomeric intermediates where water, or the same alcohol reagent, take part in assisting the proton trans-fer. Furthermore, we have analyzed the charge separated structure proposed experimentally and have found a nearly pure covalent bond between the two expected charged moieties. Finally, the Knoevenagel condensation step that generates the acrylonitrile is found to be the rate-determining step.
PMID: 30632367 [PubMed - as supplied by publisher]
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