Switching Between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) pincer complexes
W. Yang (TU Delft - ChemE/Inorganic Systems Engineering)
Ivan Yu Chernyshov (ITMO University)
M Weber (Freie Universität Berlin)
Evgeny Pidko (TU Delft - ChemE/Algemeen, TU Delft - ChemE/Inorganic Systems Engineering)
G.A. Filonenko (TU Delft - ChemE/Inorganic Systems Engineering)
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Abstract
While Mn-catalyzed (de)hydrogenation of carbonyl derivatives has been well established, the reactivity of Mn hydrides with olefins remains very rare. Herein, we report a Mn(I) pincer complex that effectively promotes site-controlled transposition of olefins. This reactivity is shown to emerge once the N–H functionality within the Mn/NH bifunctional complex is suppressed by alkylation. While detrimental for carbonyl (de)hydrogenation, such masking of the cooperative N–H functionality allows for the highly efficient conversion of a wide range of allylarenes to higher-value 1-propenybenzenes in near-quantitative yield with excellent stereoselectivities. The reactivity toward a single positional isomerization was also retained for long-chain alkenes, resulting in the highly regioselective formation of 2-alkenes, which are less thermodynamically stable compared to other possible isomerization products. The detailed mechanistic analysis of the reaction between the activated Mn catalyst and olefins points to catalysis operating via a metal–alkyl mechanism─one of the three conventional transposition mechanisms previously unknown in Mn complexes
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