om9b00102_si_002.xyz (89.88 kB)
The Importance of Metal–Ligand Cooperativity in the Phosphorus–Nitrogen PN3P Platform: A Computational Study on Mn-Catalyzed Pyrrole Synthesis
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posted on 2019-12-12, 23:29 authored by Daniel Lupp, Kuo-Wei HuangWe studied the mechanism of the pyrrole synthesis catalyzed
by
a PN3P–Mn pincer ligand system and show that a bifunctional
double hydrogen transfer mechanism is favored over the alternative
β-hydride elimination. Both dehydrogenation and hydrogen-formation
steps benefit from proton shuttles, with alcohol-mediated processes
being consistently favored, leading to energy barriers that, in good
agreement with the experimental results, are similar to those for
the previously reported corresponding iridium-catalyzed process. We
also show that the coordination of one potassium ion to the ligand
lowers the energy barriers for the key steps. The overall rate-determining
step is the regeneration of the catalyst with an energy barrier of
30.7 kcal/mol with potassium and 31.1 kcal/mol without potassium.
Our results support the involvement and the importance of the aromatization/dearomatization
paradigm in the reaction.