ArticleACS catalysis2022
Switching between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) Pincer Complexes.
Article in ACS catalysis, 2022. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 8 papers.
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Who cites it
8 citing papers in PubMed, 26 citations in OpenAlex.
- Direct Synthesis of Polyesterether from Ethylene Glycol.ACS sustainable chemistry & engineering · 2025Article
- An open-shell Ir(II)/Ir(IV) redox couple outperforms an Ir(I)/Ir(III) pair in olefin isomerization.Nature chemistry · 2025Article
- Tungsten-catalyzed stereodivergent isomerization of terminal olefins.Chemical science · 2025Article
- Alkene Isomerization Catalyzed by a Mn(I) Bisphosphine Borohydride Complex.ACS catalysis · 2024Article
- MACE: Automated Assessment of Stereochemistry of Transition Metal Complexes and Its Applications in Computational Catalysis.Journal of chemical theory and computation · 2024Article
- Hydrogenation of Terminal Alkenes Catalyzed by Air-Stable Mn(I) Complexes Bearing an N-Heterocyclic Carbene-Based PCP Pincer Ligand.Chemistry (Weinheim an der Bergstrasse, Germany) · 2024Article
- HiREX: High-Throughput Reactivity Exploration for Extended Databases of Transition-Metal Catalysts.Journal of chemical information and modeling · 2023Article
- Performance of homogeneous catalysts viewed in dynamics.Chemical communications (Cambridge, England) · 2023Review
Corrections and comments
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Authors and funding
5 authors at 3 institutions in 3 countries.
Funding
No grant is acknowledged in the PubMed record.
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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Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.